JP2003221423A - Composite resin composition and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an aliphatic-aromatic polyester composite resin material excellent in moldability and mechanical strengths, containing at least one kind of a biomass material such as cellulose, lignocellulose or starch. <P>SOLUTION: A method for producing the composite resin composition excellent in moldability and strength characteristics comprises heating and kneading or the like of the composition containing 5-95 wt.% aliphatic-aromatic polyester (component A), 95-5 wt.% cellulose, lignocellulose or starch material (component B), 0.2-30 wt.% of sum of the components A and B unsaturated carboxylic acid or derivative thereof (component C) and 0.01-2 wt.% of an organic peroxide, which are subjected to modification reaction that uses relatively predominant maleroylification of the biomass material over an adduct of the aliphatic- aromatic polyester maleic anhydride, in comparison with using a polymer having methyl group such as polypropylene or polylactic acid. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite resin composition comprising biodegradable constituents and a method for producing the same. More specifically, when molding the composition, it is suitable for extrusion molding and injection molding. It has high workability, such as
The molded products obtained have excellent mechanical strength and biodegradability, and molded products for one-way applications such as films and sheets, trays and containers, some furniture materials, building materials, interior materials and exterior materials for automobiles and home appliances. The present invention relates to a composite resin composition that can be effectively used for a housing member.

[0002]

2. Description of the Related Art Biomass substances such as cellulose, wood and starch have low thermoplasticity, and once pulverized, they cannot be molded into boards, sheets and the like. Therefore, the use of wood flour that exists in large quantities is limited to fields with low added value such as bedding substitutes for livestock breeding, dairy materials such as bedding, fillers, etc. It is incinerated without disposal.

With regard to cellulosic substances, various attempts have been made to obtain high value-added materials by imparting new properties, including plastic materials, but breakthroughs due to their progress are not always easy. It cannot be said that the effective use of waste paper is necessarily advanced, and there is a connection with the effectuation of the Recycling Law, so it is further desired to search for new utilization technologies and methods. With respect to starch, it is necessary to consider the utilization technology other than food applications as a measure for increasing the amount of starch handled by starch manufacturers because of the current balance of global demand or the room for increasing the amount of starch supply. New developments are sought after. Furthermore, stopping the use of oil is one of the major reasons,
Organic materials using plant resources and grains as raw materials, systematic development of organic polymer material manufacturing technology, and technological development have come to be taken up as one of the national research strategies in various countries around the world. In that sense, even in Japan, where such momentum is relatively poor, as a basic measure, it is necessary to have a awareness of the problem of steadily assembling technologies for utilizing biomass materials.

Regarding the above-mentioned viewpoint that the biomass has poor thermoplasticity and cannot be molded once it is pulverized, considering a countermeasure, the biomass powder is used as a filler in combination with a thermoplastic polymer. A material called "moldwood" that has the obtained molding performance emerges. Regarding the molding material obtained by melt-kneading the thermoplastic resin and the biomass powder, the dispersibility of the filler, the compatibility of the filler surface with the matrix resin, and the biomass filler surface as one of the results are conventionally known. Adhesiveness of matrix resins and insufficient mechanical properties of molded products resulting from them have been a problem, and some measures have been taken.

In order to solve these problems, the present inventor first diligently studied a biomass filler and a polyolefin composite material such as polypropylene, and introduced a modified resin into which an active group capable of reacting with a functional group on the filler surface was introduced. It has been found that such problems can be solved by adopting as a matrix resin. That is, the inventor of the present invention has disclosed in
A film, a sheet, a furniture material, which has a remarkably excellent mechanical strength obtained by blending a modified polyolefin, a cellulosic material and a specific graft body in a specific ratio in 2-39642, and also has excellent transparency and smoothness, Disclosed is a technique relating to a composite resin composition suitable for interior building materials and the like. Many studies have been conducted on the application of this technology, and artificial wood made by extrusion-molding a wood powder / thermoplastic resin composite kneaded product and having extremely high durability has been effectively used as a housing member. . These technologies use general-purpose thermoplastic resin (polypropylene, polypropylene,
Since polyethylene, polyvinyl chloride, ABS resin, etc.) is used as a matrix resin, it is extremely meaningful when a high degree of durability is recognized. However, assuming the final disposal process after the end of use of these products, there is a risk that they will remain in the environment semipermanently during landfill and that harmful substances such as dioxins will be discharged into the environment during incineration.

Therefore, in consideration of the final disposal treatment after the end of use of the product, a biodegradable resin that decomposes at the time of landfill and does not remain in the environment and does not discharge harmful substances such as dioxins at the time of incineration. A molding material made of a biomass material has been demanded. It is needless to say that the material itself needs to have physical properties such as strength properties and other functions that are actually required. Therefore, the present inventor has investigated a composite resin composition in which polylactic acid, which is a biodegradable polymer, is used as a matrix resin and is combined with a biomass filler, and has already applied for a patent. It can be said that the waste disposal property was essentially improved by this, and a composite resin composition having remarkably excellent physical properties was realized, but there are still problems due to the fact that the matrix resin is polylactic acid. That is, polylactic acid is a hard and brittle resin at room temperature, and it does not biodegrade easily when it is buried in the soil, and it is practical only after hydrolysis by the action of heat in compost. There are at least two points that biodegradation progresses. In addition to that, there is also a relationship with the former, and when a biomass-based filler is blended, the heat fluidity of the composite resin composition decreases and the molding processability decreases,
The result is that the deterioration of mechanical strength characteristics is noticeable.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a resin composition containing a biomass filler and biodegradable in soil, which is excellent in moldability and mechanical properties at low cost. An object is to provide an aliphatic aromatic polyester resin composition that can be produced. Another object of the present invention is to provide a resin composite obtained from a biodegradable resin composition containing a biomass-based filler, which is excellent in moldability and mechanical strength.

Still another object of the present invention is to propose a production method capable of producing the above-mentioned aliphatic aromatic polyester-based and further aliphatic polyester-based resin composite at low cost.

Further, one of the problems to be solved by the present invention is that when the final disposal process after the use of the product is taken into consideration, it is effective in the soil at the time of landfill disposal. Steadily biodegrades at a certain rate and does not remain in the environment,
It is an object of the present invention to provide a molding material composed of a biodegradable resin and a biomass material, which does not emit harmful substances such as dioxins to the environment at the time of incineration and has a sufficiently reduced calorific value of combustion.

Further, another one of the problems to be solved by the present invention is a biodegradable polymer having the above-mentioned characteristics, which has higher processability and is excellent in usability, in other words, an elastomer characteristic at room temperature. It is intended to provide a degradable composite resin composition by combining a biodegradable polymer having physical properties including the above and a biomass material, a method for producing the same, and a molding material comprising the degradable composite material.

Furthermore, another one of the problems to be solved by the present invention is that from disposable applications to some durable materials applications (for example, building materials, interior / exterior materials of automobiles, housings of household appliances, etc.). Etc.) and taking into account the final disposal process after the product has been used, it will not decompose and will not remain in the environment at the time of landfill, and harmful substances such as dioxins at the time of incineration. A material that does not discharge waste into the environment and molded products made of biodegradable resin and biomass materials, and molded products made by molding it, artificial wood, plate materials, pillar materials, films, sheets, foams, heat insulating materials, containers, trays, etc. To provide.

[0012]

The inventor of the present invention has conducted extensive research to solve these problems. As a result, first, in order to obtain a resin composite material excellent in molding processability and mechanical properties, an aliphatic aromatic polyester not containing a methyl group was used as a matrix resin, and an unsaturated carboxylic acid or its derivative was used as a modifier to fill the biomass. We examined heating and kneading with an agent and a radical generator (organic peroxide). At that time, the addition reaction of the above modifier to the matrix resin caused a matrix such as polypropylene or polylactic acid containing a methyl group. It was found that the reaction was suppressed more than in the case of using the resin, and the esterification reaction of the biomass component with the unsaturated carboxylic acid or its derivative (for example, maleic anhydride) suitably proceeded accordingly. This leads to an increase in the thermoplasticity of the filler biomass, which enhances the formability of the finally obtained composite material. On the other hand, the addition reaction of the modifier (maleic anhydride, etc.) to the matrix resin also progressed significantly, resulting in the grafting reaction on the biomass surface site, and the adhesiveness at the matrix resin / biomass filler interface was maintained. It is ensured and the physical properties of the finally obtained composite material are enhanced. These facts also apply in advance in the case of heating and kneading with the matrix resin, the modifier and the organic peroxide ternary mixture, and the unreacted modifier remains, which may be left during the final kneading reaction. However, this leads to an esterification reaction of biomass components, but naturally the degree of esterification is lower than in the case of batch heating and kneading of all components. As a result, the solution of the above problems has been achieved by the present invention relating to a composite from the following aliphatic aromatic polyester composition and a method for producing the same.

That is, one of the manufacturing methods of the present invention is
Group consisting of 5 to 95% by weight of aliphatic aromatic polyester (component A) synthesized by combining 1,4-butanediol and dicarboxylic acid (adipic acid and terephthalic acid), cellulose, lignocellulose and starch At least one type of biomass material (component B) 95 selected from
~ 5% by weight (however, the total amount of A component and B component is 10
0 parts by weight) and a three-part mixture of 0.2 to 30% by weight of an unsaturated carboxylic acid or its derivative (component C) with respect to 100 parts by weight of the total amount of the components A and B, the radical generator (A). 0.0 based on 100 parts by weight of the total of the components and B components
1 to 2% by weight) in the presence of heat and kneading.

Another one relating to the production method of the present invention is an aliphatic aromatic polyester (A obtained by synthesizing by combining 1,4-butanediol and dicarboxylic acid (adipic acid and terephthalic acid). Component) 100 parts by weight and unsaturated carboxylic acid or its derivative (component C) 0.2 to
50 wt% is reacted by heating in the presence of a radical generator to obtain a modified aliphatic aromatic polyester (D component), and then a mixture with a D component containing 0 to 95 wt% of the A component (E
Ingredients) 5 to 95% by weight and at least one biomass material (B component) selected from the group consisting of cellulose, lignocellulose and starch 95 to 5% by weight (however, the total amount of E and B components is 100). (Part by weight) and heating and kneading the mixture.

One of the compositions of the present invention is
5 to 95% by weight of an aliphatic aromatic polyester (component A) synthesized by combining 1,4-butanediol and a dicarboxylic acid (adipic acid and terephthalic acid), and a group consisting of cellulose, lignocellulose and starch is selected. At least one type of biomass material (B component) 95-
5% by weight (however, the total amount of the A component and the B component is 100 parts by weight), and 0.2 to 30% by weight of the unsaturated carboxylic acid or the same with respect to 100 parts by weight of the total amount of the A component and the B component. A composite resin composition prepared by heating and kneading a derivative (C component) in the presence of a radical generator, wherein at least a part of the A component and at least a part of the B component contain the C component. A composite resin composition comprising a substance covalently bound via and a B component at least partially derivatized with a C component.

Another aspect of the composition of the present invention is the aliphatic aromatic polyester obtained by combining 1,4-butanediol and dicarboxylic acid (adipic acid and terephthalic acid) (component A). ) 100% by weight and unsaturated carboxylic acid or its derivative (component C) 0.2-5
0% by weight is heated and reacted in the presence of a radical generator to obtain a modified aliphatic aromatic polyester (component D), and then a mixture (component E) with component D containing 0 to 95% by weight of component A (component E) is added. ~ 95 wt% and at least one biomass component (B component) selected from cellulose, lignocellulose and starch 95 to 5 wt% (provided that E component and B
(A total amount of the components is 100 parts by weight), which is a composite resin composition obtained by heating and kneading a mixture, wherein at least a part of the A component and at least a part of the B component are covalently bonded via the C component. The composite resin composition contains a significant amount of a substance in which at least a part of the C component and the B component are covalently bonded depending on the substance and the reaction composition conditions.

Still another aspect of the present invention is a molded product, artificial wood, plate material, column material, container, film, sheet, foam, heat insulating material formed from the composite resin composition of the present invention. There are containers and trays as typical examples of molded products.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The composite resin composition of the present invention comprises an aliphatic aromatic polyester (component A), a biomass filler (component B) and an unsaturated carboxylic acid or its derivative (C) in the presence of a radical generator. Components) are heated and kneaded together to react (one-step method), or in the presence of a radical generator, an aliphatic aromatic polyester (component A) and an unsaturated carboxylic acid or its derivative (component C). To obtain a modified aliphatic aromatic polyester resin (component D),
Next, the modified aliphatic aromatic polyester (component D)
Alternatively, it can be obtained by heating and kneading a mixture of the component A and the component A as required and the biomass filler component (component B) (two-stage method).

First, the raw materials used in the present invention will be described. The aliphatic aromatic polyester used in the present invention is obtained by polycondensing a predetermined amount of each of 1,4-butanediol, adipic acid and terephthalic acid, and is commercially available from BASF (Germany) (Germany). Ecoflex, Eastman
There are Eastar Bio of Chemical (USA) and Biomax of Dupont (USA). It is said that they have very high price competitiveness because they can use existing polyester production technology and equipment such as PET. As a biodegradable polymer, it is the lowest priced after polylactic acid from Calgill (US). It has properties similar to those of LDPE, and has high elongation at break, excellent toughness and flexibility, impact resistance, melting point in the same temperature range as LDPE, and excellent cast and inflation film moldability. Besides, completely biodegradable and composting, European standard E
It is also characterized by having food hygiene properties that have passed C90 / 128 and US FDA standards. Between these aliphatic aromatic polyesters, Ecoflex is Eastar Bio
Since it has a branched structure compared to copolyester, there is a difference that the melt viscosity is higher, and, for example,
In the case of Eastar Bio, there are also types such as Eastar Bio GP for normal use and Eastar Bio Ultra with high melt viscosity.

The biomass filler (component B) used in the present invention is at least one selected from cellulose, lignocellulose and starch. Examples of the cellulose include crushed wood pulp, mechanically chopped alpha fiber flock obtained by subjecting wood pulp to alkali treatment, cotton linter obtained from cottonseed, cotton flock, and human silk block obtained by cutting human silk. I can. Examples of lignocellulose include lignocellulosic fibers and lignocellulosic powder. Specific examples thereof include wood pulp, refiner ground pulp (RGP), papermaking pulp, waste paper, crushed wood chips, wood powder, fruit shell powder and the like. The shape of these cellulose and lignocellulosic materials is not particularly limited, and fibrous or powdery materials can be used.

Specific examples of the wood powder include crushed materials such as pine, fir, poplar, bamboo, bagasse, and oil palm tree trunk, saw dust, and canna dust, and the fruit shell powder includes walnut, peanut, and palm. There are crushed fruits. When wood powder is used, it is preferable that the powder is pulverized as much as possible to eliminate the entanglement of the fibers, but the work is complicated.
In consideration of economy, a mesh having a mesh size of 20 to 400 is usually used. Among these, it is particularly preferable to use cellulose fiber powder, RGP or wood powder. When cellulose fiber powder or RGP is used, it is preferable to use dry defibration or the like to loosen the entanglement between the fibers.
Specific examples of starch include, for example, corn starch,
Potato starch, potato starch, tapioca starch and their lightly acetylated products can be widely used.

The unsaturated carboxylic acid or its derivative (C) used in the present invention is, for example, maleic acid, maleic anhydride, nadic acid anhydride, itaconic acid, itaconic anhydride,
Citraconic acid, citraconic anhydride, crotonic acid, isocrotonic acid, mesaconic acid, angelic acid, sorbic acid and acrylic acid are preferred, and maleic anhydride is particularly preferred. As the unsaturated carboxylic acid derivative, the above-mentioned unsaturated carboxylic acid metal salt, amide, imide, ester or the like can be used. Two or more kinds of these unsaturated carboxylic acids or anhydrides can be mixed and used.

The radical generator used in the present invention is not particularly limited as long as it accelerates the reaction between the aliphatic aromatic polyester (component A) and the unsaturated carboxylic acid or its derivative (C). For example, benzoyl peroxide, lauroyl peroxide, cumene peroxide, α ′, α′-bis (t-butylperoxydiisopropyl) benzene, di-t-butyl peroxide, 2,
5-di (t-butylperoxy) hexane, p-chlorobenzoyl peroxide, 1,1-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butylperoxypiperate, t-butylperoxy Oxy-2
-Ethyl hexanoate, t-butyl peroxybenzoate, bis (4-t-butylcyclohexyl) peroxydicarbonate, diisopropyl peroxydicarbonate, t-butyl peroxyisopropyl carbonate, dicumyl peroxide, 2, 5-dimethyl-2,
Examples thereof include peroxides such as 5-di (t-butylperoxy) hexane and azohi compounds such as azobisisobutyronitrile. Among these, dicumyl peroxide, t-butyl peroxybenzoate,
2,5-Dimethyl-2,5-di (t-butylperoxy) hexane is preferred. Such organic peroxides can be used alone or in combination of two or more.

Next, embodiments of the method for producing the composite resin composition of the present invention will be described in detail. One of the production methods of the present invention is an aliphatic aromatic polyester resin component (A component), a biomass filler component (B component) and an unsaturated carboxylic acid or its derivative (C) in the presence of a radical generator.
This is a method (one-step method) of heating and kneading the components) together. Here, the ratio of the A component and the B component is 5 to 95% by weight, preferably 10 to 90% by weight in the A component and the B component.

If the proportion of the component A exceeds 95% by weight, the proportion of the component B becomes too small, and the effect due to the presence of the filler such as the reinforcing effect of the component B is lowered, which is not preferable. On the other hand, when the proportion of the component A is less than 5% by weight, the proportion of the component B becomes too large, so that a molded product having a problem with strength or a molded product having many problems such as poor gloss is obtained. It is not preferable.

The amount of component C is 0.2 to 30% by weight based on 100 parts by weight of the total amount of components A and B. In this case, if the amount of the C component is less than 0.2% by weight, a substance in which the A component and the B component are bound via the C component and a B component derivatized with the C component cannot be obtained or obtained. However, the amount is not sufficient, and the strength of the molded product when processed into a molded product is less than expected, and the heat fluid processability during processing is also less than expected. As described above, this is because when the three components, component A, component B and component C, are heated and kneaded together in the presence of the radical generator, the modification of component A and the esterification reaction of component B occur simultaneously. In the case of the component A of the present invention, hydrogen radicals are easily abstracted by the radical generator and there is no methyl group on the component A that easily causes radicals. The modification by the component is suppressed, and accordingly, the esterification of the B component by the C component (maleroylation when the modifying agent is maleic anhydride) progresses more than that when the A component is polypropylene or polylactic acid having a methyl group, It is based on the result of the thermoplasticization of the B component.

Incidentally, the literature (John, J., Tang, J., Ya
ng, Z., Bhattacharya, M: J, Polym, Sci., Part A, P
According to olym, Chem., 35 (6), 1139-1148 (1997)), polycaprolactone (PCL), which is a polyester having no methyl group similar to the component A, is used together with maleic anhydride and dicumyl peroxide. When kneading with heat, P
It is true that the radical addition of maleic anhydride to CL takes place, and that it leads to hydrogen abstraction from methylene (in the α-position) adjacent to the carboxyl group of PCL and subsequent β-cleavage to the resulting PCL terminal chain. Has been shown to occur by the addition of maleic anhydride and subsequent recombination. Hydrogen abstraction from the methylene group here is
Compared to that from the methyl group, it clearly requires more energy and is relatively unlikely to occur. Further, when the amount of the C component exceeds 30% by weight, further mechanical strength cannot be obtained and it tends to be rather brittle. The amount of the radical generator is not particularly limited, and is 0.01 to 2% by weight with respect to 100 parts by weight of the component A.

In the manufacturing method of the present invention, the method of heating and kneading is a conventionally known method, for example, a mixer such as a Humberley mixer or a Henschel mixer, a roll mill equipped with a plurality of rolls, a kneader, and various extruders. Using an (extruder), a temperature equal to or higher than the melting point of the component A, preferably 120 to 240 ° C, more preferably 140 to 200 ° C.
At a temperature of 5 to 60 minutes, preferably 10 to 40 minutes. Temperatures high enough to burn the B component should be avoided. Also, the rotation speed of the kneader etc. at this time is usually
20 to 200 rpm, preferably 30 to 150 rpm.
The order of adding the above components during heating and kneading is not particularly limited. Generally, it is preferable to add all components in advance after mixing them well, or to add the components B and C to the molten state of the component A. Further, during this heating and kneading, it is preferable to carry out in an inert gas atmosphere so that moisture and oxygen (air) do not enter from the outside of the system, while substituting with an inert gas or bubbling with an inert gas. You can go while.

Another production method of the present invention is the aliphatic aromatic polyester (component A) in the presence of a radical generator.
And an unsaturated carboxylic acid or its derivative (component C) are heated and reacted to modify an aliphatic aromatic polyester (component D)
And then kneading the modified aliphatic aromatic polyester resin (component D) or a mixture of the aliphatic aromatic polyester resin (component A) (component E) and the biomass filler (component B) with heating. Method (two-step method).

In this case, the amount of the component C and the amount of the radical generator with respect to the amount of the component A are the same as in the one-step method described above. A
The method of reacting the component with the C component can be performed by the same method as the above-mentioned heating and kneading method. Further, the A component and the C component can be reacted in the presence of a solvent. In this case, it is preferable to use a solvent having a high boiling point that dissolves the component A. The reaction temperature is 120 to 240 ° C., preferably 140 to 200.
In the case of the heating and kneading method, the reaction time is 5 to 60 minutes,
It is preferably 10 to 40 minutes, and 30 minutes to 5 hours in the case of using a solvent. In the latter case, after the reaction,
The solvent is removed by a known method such as distillation or reprecipitation to obtain the D component.

The obtained D component is heated as it is with the B component,
Although kneading may be performed, a mixture (E component) obtained by diluting the D component with the unmodified A component may be used, if necessary, in consideration of the mixing ratio of the B component and the D component. That is, a mixture of the D component and the A component (E component) containing 0 to 95% by weight of the A component may be used. The method of heating and kneading the component D or E and the component B can also be performed by the same method as the one-step method. In this case, the ratio of the D component or E component to the B component is 2.5 to 95% by weight of the D component or E component, preferably 5
Is about 90% by weight. Here, if the ratio of the D component or the E component exceeds 95% by weight, the ratio of the B component becomes too small, and the reinforcing effect of the B component decreases, which is not preferable. On the other hand, when the ratio of the D component or the E component is less than 2.5% by weight, the ratio of the B component becomes too large, so that a molded product having a problem in strength can be obtained, and the appearance such as gloss is apparent. This is not preferable because a molded product having the advantages thereof can be obtained.

In the method for producing the composite resin composition of the present invention and various molding methods described later, various additives such as a lubricant, an antioxidant, a colorant, an antistatic agent and a plasticizer are appropriately added if necessary. You can The composite resin composition thus obtained is excellent in mechanical strength during molding and heat fluid processability, has biodegradability, and gives a molded article excellent in smoothness, gloss, and texture.

In the composite resin composition of the present invention, at least a part of the aliphatic aromatic polyester resin (component A) and at least a part of the biomass filler (component B) are unsaturated carboxylic acid or its derivative (C). Component), and at least a part of the biomass filler (B component) is plasticized by a significant amount of ester bond with the unsaturated carboxylic acid or its derivative (C component). The presence of them contributes to the above-mentioned various properties, and particularly contributes to enhancement of tensile strength and improvement of heat fluid processability when the composite resin composition of the present invention is processed into a molded product.

The composite resin composition of the present invention can be appropriately molded into desired shapes by various means such as pressure molding, film molding, vacuum molding, extrusion molding and injection molding to produce various molded products. . Therefore, the industrial applicability of the composite resin composition according to the present invention is extremely high. That is, according to the present invention, when various properties are excellent and the final disposal process after the end of use of the product is taken into consideration, it does not decompose and does not remain in the environment at the time of landfill, and it is harmful when incinerated. Molded products, artificial wood, films, which do not release substances into the environment
Sheets, foams, trays, containers, etc. can be provided.

The composite resin composition according to the present invention is used in various films, sheet materials, and disposable molded products (for example, containers, pipes, squares, bars, artificial wood, trays,
Materials such as concrete panels, foam, etc.), furniture, building materials, automobile interior materials, automobile exterior materials, housings for home appliances, civil engineering and construction materials, agricultural / dairy agriculture / fishery materials, recreation materials, sports materials, etc. Can be effectively used as. In this way, not only is it possible to make advanced use of biomass materials that have been low in added value until now,
A composite resin composition having excellent strength properties and high moldability and biodegradability can be provided industrially easily and at a relatively low cost.

[0036]

EXAMPLES Examples of the present invention will be described below. The methods for measuring physical properties used in this example are as follows. 1) Tensile strength (breaking), tensile breaking elongation, tensile elastic modulus (Young's modulus) ... Measured by an autograph manufactured by Shimadzu Corporation according to JISK-6732. 2) Melt viscosity, melting temperature ... Measured with a flow tester CFF-C manufactured by Shimadzu Corporation.

Production Example 1 Aliphatic Aromatic Polyester (Copolyester Combining 1,4-Butanediol and Dicarboxylic Acid (Adipic Acid and Terephthalic Acid); Eastman Chemical Company (US))
Eastar Bio GP copolyester) 23 g, maleic anhydride 2.3 g and dicumyl peroxide 0.08 g
Are weighed in a beaker and mixed well, then the temperature is adjusted to 160 ° C, and the stirrer blades rotate in opposite directions at 30 rpm. Toyo Seiki Co., Ltd. Lab Blast Mill 3
The entire amount was quickly charged into a 0 ml kneading die. After input,
Immediately, increase the rotating speed of the stirrer blade to 70 rpm, and
Kneading reaction was carried out at 0 ° C. for 15 minutes. Immediately after completion of the reaction, the contents were taken out and cooled. After being sufficiently cooled, it was once hot-press molded into a thin-film sheet and then made into pieces. In subsequent experiments, maleic anhydride-modified aliphatic aromatic copolyester (MEB-
It was tested as 1). After taking a part of the obtained MEB-1 and dissolving it in chloroform and adding and precipitating it in a large excess of n-pentane, and then purifying by filtration and drying, infrared absorption spectroscopy ( FTIR) and nuclear magnetic resonance analysis (NMR) were performed to confirm the addition of maleic anhydride to the aliphatic aromatic copolyester resin. The obtained kneaded material (MEB-1) was deformed under pressure at 180 ° C. for 0.5 minutes to prepare a film having a thickness of 0.4 mm. 80 mm x 5 mm strip specimens were cut out from this film and evaluated for mechanical properties and thermal fluid properties.
The tensile strength was 19.2 MPa, the Young's modulus was 33.6 MPa, the elongation at break was 987.6%, the temperature was 180 ° C., the melt viscosity under a load of 50 kgf / cm ^{2 was} 2180 poise, and the heat flow temperature was 123.1 ° C. The untreated aliphatic aromatic copolyester resin (control) had a tensile strength of 20.8 MPa, a Young's modulus of 34.6 MPa, and a breaking elongation of 1154.4%, 180.
Melt viscosity under load of 50 kgf / cm ^{2 at} ℃ 2205 pois
e, the heat flow temperature was 124.5 ° C.

Comparative Example 1 Aliphatic Aromatic Polyester (Copolyester Combining 1,4-Butanediol and Dicarboxylic Acid (Adipic Acid and Terephthalic Acid); Eastman Chemical Company (US) E
astar Bio GP copolyester) and cellulose fiber powder (KCF (Kishi Flock) W-made by Nippon Paper Industries Co., Ltd.)
100) and 13.0 g each were weighed in a beaker, mixed well with a spatula, and then adjusted to 180 ° C.,
5 in a Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.) in which the stirrer blades rotate in opposite directions at a rotation speed of 30 rpm.
The mixture was added over a period of time, and subsequently the number of revolutions was increased to 70 rpm and kneading was performed for 15 minutes. Then, the obtained kneaded product is subjected to pressure molding at 180 ° C. for 0.5 minutes to obtain 0.4.
A mm-thick film was prepared. 80mm from this film
A × 5 mm strip-shaped test piece was cut out and evaluated for its mechanical properties (tensile strength properties) and heat flow properties. The results were as follows. That is, tensile strength 14.1 MPa, tensile elastic modulus 452.2 MPa, elongation at break 13.8%, 180
℃, melt viscosity 4731 poise under 50kgf / cm ² load,
The heat flow temperature was 125.7 ° C.

Example 1 11.7 g of an aliphatic aromatic polyester (Eastar BioGP copolyester manufactured by Eastman Chemical Company (US) in which 1,4-butanediol and dicarboxylic acids (adipic acid and terephthalic acid) were combined), Production Example 1 Maleic anhydride-modified aliphatic aromatic copolyester prepared in (MEB-1)
1.3 g and cellulose fiber powder (K, manufactured by Nippon Paper Industries Co., Ltd.)
CFW-100) (13 g) was weighed in a beaker, mixed well with a spatula, and then temperature-controlled at 180 ° C., and a stirring frame blade was rotated in opposite directions at a rotation speed of 30 rpm. Labo Plastomill (Toyo Seiki ( Co., Ltd.) for 5 minutes, and then the rotation speed is increased to 70 rpm to 1
Kneading was performed for 5 minutes.

Then, the kneaded material thus obtained was dried at 180.degree.
The film was pressure molded for 5 minutes to prepare a film having a thickness of 0.4 mm. 80 mm × 5 mm strip-shaped test pieces were cut out from this film and evaluated for mechanical properties (tensile strength properties) and heat flow properties. The results are as follows: tensile strength 16.0 MPa, tensile elastic modulus 237.8 MPa, elongation at break 26.5%, 180
℃, melt viscosity under load of 50kgf / cm ² 3565 poise,
The heat flow temperature was 124.8 ° C. Comparing these results with the corresponding values of the copolyester and cellulose fiber powder of Comparative Example 1 directly kneaded and complexed without addition of the modified copolyether, the most noticeable result is that the tensile elastic modulus is small. . The maleic anhydride-modified copolyester was produced as shown in Production Example 1 and used as it was without purification, but it was known that a significant amount of unreacted maleic anhydride residue remained. Has been. The presence of a section acting as a low molecular weight plasticizer, and the effect of esterifying the cellulose filler at the time of kneading in this example to plasticize it even if it is its surface phase is considered to enhance the elastomeric property of the composite. Can be said. As a result, the elongation at break is in Comparative Example 1
, Which was 13.8%, doubled to 26.5%. The melt viscosity is also decreasing. Nevertheless, the tensile strength of Comparative Example 1 was 14.1 MPa, but
Based on the increase of 6.0 MPa, the maleic anhydride-modified copolyester is chemically bonded to the hydroxyl group on the surface of the cellulose filler, and the adhesiveness at their interface is increased by the graft polymerization (modification) of the former to the latter. This means that the composite strength enhancing action was recognized. In order to substantiate these arguments, the following experiment of Example 2 and further experiment of Example 4 were performed.

Example 2 Aliphatic aromatic polyester (Eastar Bio GP Copolyester) and its maleic anhydride-modified product were each added to 1
A composite resin composition was prepared in the same manner as in Example 1 except that the amounts were 0.4 g and 2.6 g, and the physical properties were measured. As a result, the tensile strength was 18.2 MPa, the tensile elastic modulus was 211.2 MPa, the elongation at break was 30.8%, 180 ° C., the melt viscosity under load of 50 kgf / cm ^{2 was} 3107.0 poise, and the heat flow temperature was 123.8 ° C. Although the value is obtained, it is in accordance with the above discussion and consideration.

Example 3 A composite resin composition was prepared in the same manner as in Example 1 except that corn starch was used as the filler instead of the cellulose fiber powder, and the physical properties were measured. As a result, the tensile strength was 15.3.
MPa, tensile elastic modulus 203.6 MPa, elongation at break 20.4
%, 180 ° C, melt viscosity 262 under load of 50 kgf / cm ²
Characteristic values of 1.0 poise and a heat flow temperature of 123.7 ° C. were obtained.

Example 4 Aliphatic Aromatic Polyester (Copolyester Combining 1,4-Butanediol and Dicarboxylic Acid (Adipic Acid and Terephthalic Acid); Eastman Chemical Company (USA) Eas
tar Bio GP copolyester) 13.0 g, cellulose fiber powder (Nippon Paper Industries KCFW-100) 13.0 g,
1.3 g of maleic anhydride and dicumyl peroxide.
Weigh 2g into a beaker, mix well with a spatula, and then adjust the temperature to 180 ° C with a stirring blade of 30 rpm.
The mixture was placed in a Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.) rotating in opposite directions at a rotation speed of 5 minutes for 5 minutes, and then the rotation speed was increased to 70 rpm for 15 minutes of kneading. Then, the obtained kneaded product was pressure-molded at 180 ° C. for 0.5 minutes to prepare a film having a thickness of 0.4 mm. Cut a 80mm x 5mm strip test piece from this film,
The mechanical properties (tensile strength properties) and the heat flow properties were evaluated. The result is a tensile strength of 20.4 MPa and a tensile modulus of 14
8.5MPa, elongation at break 37.6%, 180 ℃, 50kgf
The melt viscosity under a load of / cm ^{2 was} 2962.5 poise, and the heat flow temperature was 124.0 ° C. This result also shows that in the case of the one-step method, the adhesiveness between the filler and the matrix resin interface by the action of the modified product of the aliphatic or aromatic polyester by maleic anhydride is enhanced, and the increase in the strength based on it is further recognized. The effect of esterification (maleroylation) of cellulose fiber powder with acid and the greater increase in thermoplasticity and molding processability of the composite due to it is clearly recognized. Compared to the similar study results using polypropylene or polylactic acid as the matrix resin and cellulose or lignocellulose as the filler, the plasticization of the composite and the increase in the molding processability based on it are more distinct and significant. The result has been recognized as a thing.

From the above results, an aliphatic aromatic copolyester (component A), a biomass filler such as cellulose fiber powder (component B), and maleic anhydride (component C) are heated and kneaded in the presence of a radical initiator. It was thus known that a composite resin composition having particularly excellent strength characteristics and good moldability could be obtained. In the composite material, it was first pointed out that the maleic anhydride-modified copolyester functions as a reactive compatibilizer. That is, the maleroyl group in the maleic anhydride-modified copolyester and the hydrogen group on the surface of the biomass filler react while kneading at 180 ° C. for 20 minutes, and the ester bond causes the maleic acid to coexist on the surface of the biomass filler via maleic acid. The polyester is grafted resulting in increased adhesion at the interface between the biomass filler and the matrix resin copolyester in the final molding. On the other hand, maleic anhydride (component C) can simultaneously esterify the biomass filler component (component B), increasing its thermoplasticity and enhancing the elastomeric properties of the final product. This leads to an increase in elongation at break, a decrease in elastic modulus, and a decrease in melt viscosity.

What has been clearly found in the present invention is that
When the component is copolyester of Eastar Bio type, the esterification of the latter biomass filler progresses significantly more than when using PP or polylactic acid as the A component. It was considered that the hydrogen radical abstraction was more difficult in the case of the copolyester here than in the case of PP or polylactic acid, and the addition of maleic anhydride to them was suppressed.
That is, the former has a methyl group, and hydrogen abstraction from it becomes a problem, whereas the latter copolyester requires hydrogen abstraction from a methylene group, which requires more energy and requires the same conditions. Then, the occurrence was suppressed.

[0046]

As described above, according to the present invention, when it is disposed of in the soil, it is steadily decomposed at an effective rate and does not remain in the environment, and when incinerated, harmful substances such as dioxins are discharged to the environment. , A resin composition consisting of a biodegradable resin and a biomass material with a sufficiently reduced combustion calorific value, which is excellent in moldability and mechanical properties, and is particularly harmful when the matrix resin is polylactic acid. Thus, it has become possible to obtain an aliphatic-aromatic polyester-based composite material that solves the above problem at low cost.

   ─────────────────────────────────────────────────── ─── Continued front page    (71) Applicant 502040052             Jesack Trading Co., Ltd.             2-21-10 Yoyogi, Shibuya-ku, Tokyo (72) Inventor Nobuo Shiraishi             13-3 Shimogamogucho Tamachi, Sakyo-ku, Kyoto F-term (reference) 4F071 AA09 AA44 AA73 AC09 AF15                       AF20 AF21 AH01 AH03 AH04                       AH05 AH11 AH12 BA01 BB03                       BB05 BB06 BC01 BC04 BC06                 4J026 AA02 AA03 AA04 AB07 AC18                       BA24 BA25 BA33 BA35 BB01                       DB07 DB15 DB32 GA07 GA08                 4J029 AA03 AB04 AB07 AE01 AE03                       BA05 CA06 CB06A GA12                       GA13 GA15 GA16 GA17 GA41                       GA42 GA43 KD02 KH01 LA20

Claims (18)

[Claims] 1. An aliphatic aromatic polyester (component A) synthesized by combining 1,4-butanediol and a dicarboxylic acid (adipic acid and terephthalic acid) in an amount of 5 to 95% by weight.
And at least one biomass material selected from the group consisting of cellulose, lignocellulose and starch (B
Component) 95 to 5% by weight (however, the total amount of the A component and the B component is 100 parts by weight), and the total amount of the A component and the B component is 10
A ternary mixture of 0.2 to 30% by weight of an unsaturated carboxylic acid or a derivative thereof (component C) with respect to 0 parts by weight is used as a radical generator (0 with respect to 100 parts by weight of the total amount of the components A and B). 0.01 to 2% by weight) in the presence of heat and kneading. 2. An aliphatic aromatic polyester (component A) 10 obtained by synthesizing a combination of 1,4-butanediol and a dicarboxylic acid (adipic acid and terephthalic acid).
0 part by weight and 0.2 to 50% by weight of an unsaturated carboxylic acid or its derivative (component C) are heated and reacted in the presence of a radical generator to obtain a modified aliphatic aromatic polyester (component D), 5 to 95 wt% of a mixture (E component) with D component containing 0 to 95 wt% of A component, cellulose,
Heating and kneading a mixture of 95 to 5% by weight of at least one biomass material (B component) selected from the group consisting of lignocellulose and starch (however, the total amount of E component and B component is 100 parts by weight). A method for producing a composite resin composition comprising: 3. An unsaturated carboxylic acid or its derivative (C
The method for producing a composite resin composition according to claim 1 or 2, wherein the component) is maleic acid or maleic anhydride (maleic anhydride). 4. An aliphatic aromatic polyester (component A) synthesized by combining 1,4-butanediol and a dicarboxylic acid (adipic acid and terephthalic acid) 5-95% by weight
And at least one biomass material selected from the group consisting of cellulose, lignocellulose and starch (B
Component) A mixture of 95 to 5% by weight (however, the total amount of A component and B component is 100 parts by weight), and 0.2 to 30% by weight of unsaturation per 100 parts by weight of the total amount of A component and B component. A composite resin composition prepared by heating and kneading a carboxylic acid or a derivative thereof (component C) in the presence of a radical generator, the composite resin composition comprising at least part of component A and at least part of component B. A substance covalently bound via the C component and B at least partially derivatized with the C component
A composite resin composition containing components. 5. An aliphatic aromatic polyester (component A) 100 obtained by combining 1,4-butanediol and dicarboxylic acid (adipic acid and terephthalic acid) in combination.
% By weight and unsaturated carboxylic acid or its derivative (component C)
0.2 to 50% by weight is heated and reacted in the presence of a radical generator to obtain a modified aliphatic aromatic polyester (D component), and then a mixture with a D component containing 0 to 95% by weight of the A component (E Component) 5 to 95% by weight and at least one biomass component (B component) selected from cellulose, lignocellulosic and starch 95 to 5% by weight (however, the total amount of E component and B component is 100 parts by weight). A composite resin composition obtained by heating and kneading a mixture of
At least a part of the A component and at least a part of the B component,
A composite resin composition comprising a substance covalently bound via a component C and a significant amount of a substance covalently bound to at least part of the component C and the component B depending on reaction composition conditions. 6. The composite resin composition according to claim 4, wherein the unsaturated carboxylic acid or its derivative (component C) is maleic anhydride. 7. A molded product made of the composite resin composition according to claim 4. 8. A molded article obtained by injection molding the composite resin composition according to claim 4 or 5. 9. A molded product obtained by subjecting the composite resin composition according to claim 4 or 5 to heat extrusion molding. 10. An artificial wood comprising the composite resin composition according to claim 4. 11. A plate material comprising the composite resin composition according to claim 4. 12. A pillar material comprising the composite resin composition according to claim 4. 13. A film comprising the composite resin composition according to claim 4. 14. A sheet made of the composite resin composition according to claim 4 or 5. 15. A foam comprising the composite resin composition according to claim 4. 16. A heat insulating material comprising the composite resin composition according to claim 4 or 5. 17. A container made of the composite resin composition according to claim 4 or 5. 18. A tray comprising the composite resin composition according to claim 4.