JP2013224394A - Biodegradable resin composite composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition which is remarkably improved in the processability and dispersibility of waste paper in a biodegradable resin composite material including a large amount of waste paper mixed to a biodegradable resin.SOLUTION: A biodegradable resin composite composition is composed of a resin composite material having waste paper mixed to a biodegradable resin, in which 30-60 wt.% of waste paper having a grain size of 3-0.01 mm and 0.1-5 wt.% of an organic titanate represented by general formula (wherein R represents 12-22C alkyl or alkenyl, and m represents 0 or an integer of 1-10) are mixed.

Description

  The present invention relates to a composite composition in which waste paper is blended with a biodegradable resin, and in particular, provides a composition in which the processability and the dispersibility of waste paper are remarkably improved. To do.

In recent years, biodegradable resins have been actively developed from the viewpoint of environmental conservation. However, biodegradable resins generally have poor mechanical strength, heat resistance, and moldability, and have improved physical properties and economy. The improvement of is extremely important.
In order to improve physical properties and economic efficiency, biodegradable resin composite compositions in which fillers of inorganic fillers such as plant fibers, talc, mica, calcium carbonate, etc. are blended with biodegradable resins have been intensively developed. It is coming.

Cellulose fibers such as waste paper are blended with biodegradable resin to reinforce physical properties such as impact resistance, rigidity, mechanical strength, heat resistance, dimensional stability, etc., and biodegradability. Studies are also underway on composite materials that improve the efficiency and economic efficiency.
However, when waste paper containing no lignin or starch is added to the biodegradable resin as a compounding material, the fluidity of the composite composition is lowered, the moldability is remarkably lowered, the composite composition is made brittle, and the surface There is a problem that the uniformity and smoothness of the appearance are impaired.

Especially when a large amount of waste paper is blended, the influence of the properties of the waste paper surface is significant, and it is important how the affinity of the highly polar waste paper surface with the biodegradable resin that is the matrix is maintained. The bond strength between the matrix and the used paper surface greatly contributes to the mechanical strength, and it may be preferable to use a coupling agent that joins the used paper surface and the matrix.
Furthermore, a molded product containing a large amount of waste paper tends to be brittle. In addition, the waste paper tends to concentrate on the outer periphery of the molded product, making it difficult to perform precision processing, and the waste paper particles appear on the surface of the molded product to significantly impair the surface state or appearance of the molded product, and the gloss is impaired. Or

In order to solve the above-mentioned problems of biodegradable resin composite compositions, it is necessary to use additives such as cross-linking materials and lubricants. Conventionally, for these purposes, isocyanate resins and organic par Attempts have also been made to examine crosslinking agents such as oxides and coupling agents such as silane, titanate and aluminate.
Patent Document 1 attempts a composite agent in which a silane coupling agent is blended with a biodegradable resin and plant fiber. Patent Document 2 discloses a technology for blending a polysilane and a natural fiber with a silane coupling agent. Patent Document 3 discloses a material for blending a thermoplastic resin and a starch-based material with a titanate, silane, or aluminate coupling agent. The development of has been tried.
However, these conventionally used coupling agents have a hydrolytic group such as an organic functional group and an alkoxy group on a metal atom such as titanium, silicon, and aluminum, and the organic functional group is compatible with the matrix. However, the hydrolyzable group is hydrolyzed and chemically bonded to the additive surface to couple the composite composition, but the hydrolyzable group having 1 to 3 carbon atoms is used due to the reaction rate. However, there is still room for improvement in workability, such as the need for heat treatment to remove alcohol and the like in the reaction product.
JP 2008-208194 A JP 2008-150599 A JP 2004002613 A

  The object of the present invention is to eliminate the above-mentioned various disadvantages found in biodegradable resin composite compositions containing waste paper, particularly biodegradable resin composite compositions containing a large amount of waste paper powder. There is.

（ここで、Ｒは炭素数１２〜２２のアルキル基またはアルケニル基、ｍは０または １〜１０の整数を示す。）
で表される有機チタネートが０．１〜５重量％配合された生分解性樹脂複合材組成物が、上記の欠点を解消することが可能であることを発見し、本発明を完成した。In the resin composite material in which waste paper is blended with biodegradable resin, the present inventors have a general formula of waste paper having a particle size of 3 to 0.01 mm and 30 to 60% by weight.

(Here, R represents an alkyl or alkenyl group having 12 to 22 carbon atoms, and m represents 0 or an integer of 1 to 10.)
It was discovered that a biodegradable resin composite composition containing 0.1 to 5% by weight of an organic titanate represented by the above can solve the above-mentioned drawbacks, and the present invention has been completed.

  That is, the present invention is characterized in that biodegradable resin is blended with 30 to 60% by weight of waste paper having a particle size of 3 to 0.01 mm, and further 0.1 to 5% by weight of special organic titanate. The present invention relates to a resin composite composition.

  According to the present invention, mechanical properties such as impact resistance and rigidity, heat resistance, and physical properties such as dimensional stability are reinforced, tough, rich in molding processability, and excellent in biodegradable resin with good surface properties. A composite composition can be provided.

  The biodegradable resin referred to in the present invention is not particularly limited, and polylactic acid, polyglycolic acid, polybutylene succinate, polyvinyl alcohol and the like are applied. In particular, polylactic acid can be suitably applied.

In the present invention, waste paper is blended into the biodegradable resin. The used paper of the present invention roughly pulverizes paper and paper products collected as a papermaking raw material, drys as necessary, and / or sorts out impurities such as metals, and finely pulverizes to a particle size of 3 to 0.01 mm. 30 to 60% by weight of the finished paper powder is blended.
Paper powder having a particle size exceeding 3 mm tends to cause defects in the surface smoothness and appearance of the molded product, and tends to agglomerate and deteriorate dispersibility when made finer than 0.01 mm.
When the amount of the used paper exceeds 60% by weight, the moldability is deteriorated, the amount of the coupling agent needs to be increased, and the mechanical strength tends to be lowered. A blending amount lower than 30% by weight is not preferable because the effect of improving biodegradability and economy is hindered.

In the composition of the present invention, the organic titanate represented by the above general formula having the effect of improving fluidity, improving moldability and workability, and further improving dispersibility of waste paper is the carbon number of R Is an alkyl group or an alkenyl group of 12 to 22, and examples thereof include tetralauryl titanate, tetramyristyl titanate, tetracetyl titanate, tetrastearyl titanate, tetrabehenyl titanate, tetraoleyl titanate, tetralinolel titanate and the like. Titanate is preferably used.
Even if m of the general formula is a condensate having 1 to 10, it does not matter.
The compounding amount of the organic titanate represented by the above general formula is suitably used in the range of 0.1 to 10% by weight, and particularly preferably 1 to 5% by weight.
When the amount is less than 0.1% by weight, the intended purpose of blending is not achieved. On the other hand, when the amount exceeds 10% by weight, no special effect is exhibited, and it is determined by economic constraints.

In order to produce the composition of the present invention, it is preferable to mix the waste paper and the organic titanate in the biodegradable resin, after mixing the waste paper and the organic titanate, and then blend in the biodegradable resin. In addition, it is possible to mix three types of waste paper, organic titanate and biodegradable resin at the same time.
For mixing, a conventional mixing method is applied, and after dry blending, the mixture is kneaded (pelletized) with a single-screw or twin-screw extruder and supplied to a desired extruder or injection molding machine, or directly extruded, or It can be kneaded and molded with an injection molding machine.

  When producing various molded products by injection molding or extrusion molding using the composite material composition of the present invention, crosslinking agents such as isocyanate resins and organic peroxides generally used to improve moldability, Further, lubricants such as fatty acids, fatty acid amides, fatty acid metal salts, and higher alcohols can be added to the composite material composition of the present invention.

  Next, it demonstrates still in detail according to an Example. In addition, this invention is not limited to a following example.

Example 1
For 100 parts of waste paper powder that was coarsely crushed to 5-10 mm with a rotary cutter MRC-3050 manufactured by Miike Kogyo Co., Ltd. and finely crushed to an average particle size of 1 mm ± 0.5 mm with a turbo mill MTM-600 And 55% by weight of a mixture prepared by mixing 5 parts of tetrastearyl titanate manufactured by Mitsubishi Gas Chemical Co., Ltd. with a Henschel mixer (FM-150 manufactured by Nihon Coke Kogyo Co., Ltd.) and polylactic acid ("Terramac PL-01" manufactured by Unitika) 45% by weight of polylactic acid powder obtained by pulverizing to an average particle diameter of 1 mm ± 0.5 mm with a turbo mill was mixed with a Henschel mixer. The mixture from the mixer was extruded with a biaxial extruder 2TR-50 manufactured by Moriyama Co., Ltd. to obtain pellets having a diameter of 2 mm and a length of 3 mm.
Using these pellets, the strength and fluidity were measured with an injection molding machine PS40 manufactured by Nissei Plastic Industry at a cylinder temperature of 200 ° C. A test piece of 80 mm * 10 mm * 4 mm was manufactured, and using this test piece, tensile strength, bending strength, and bending elastic modulus were measured by an autograph AG-10TD manufactured by Shimadzu Corporation. The Izod impact value was measured using an Izod impact tester manufactured by Toyo Seiki. Furthermore, in order to measure fluidity, a spiral flow mold was used, and a flow length (cm) of width 10 mm * thickness 2 mm was measured at an injection pressure of 100 MPa.
The measurement results of each physical property value are shown in Table 1.

Example 2
The physical properties of fluidity and strength were obtained in the same manner as in Example 1 using pellets of a blend of polylactic acid and waste paper produced in the same manner as in Example 1 except that the amount of tetrastearyl titanate was 10 parts. Was measured.
The results are shown in Table 1.

Comparative Example 1
In the same manner as in Example 1, 55% by weight of pulverized waste paper powder and 45% by weight of polylactic acid in Example 1 were mixed, pellets and test pieces were prepared in the same manner as in Example 1, and physical properties were measured. did.
The results are shown in Table 1.

Table 1

Example 3
Using the same apparatus as in Example 1, the used paper is roughly pulverized to 5 to 10 mm, pulverized to a mean particle size of 1 mm ± 0.5 mm by a fine pulverizer, and further pulverized to a mean particle size of 0.5 mm ± 0.05 mm. Example 1 A mixture of 55% by weight of a mixture of 5 parts of tetrastearyl titanate and 45% by weight of polybutylene succinate (“GSPla” manufactured by Mitsubishi Chemical) was mixed with 100 parts of crushed waste paper powder. In the same manner as above, extrusion was performed with a twin screw extruder to obtain pellets having a diameter of 2 mm and a length of 3 mm. Using this pellet, a test piece was produced in the same manner as in Example 1, and the physical properties were measured. The results are shown in Table 2.

Comparative Example 2
Pellets and test pieces produced in the same manner as in Example 2 were prepared by mixing 55% by weight of the crushed waste paper powder as in Example 2 and 45% by weight of polybutylene succinate, and values of physical properties were obtained. Was measured. The results are shown in Table 2.

Table 2

Claims (1)

In a resin composite material in which waste paper is blended with biodegradable resin, waste paper having a particle size of 3 to 0.01 mm is 30 to 60% by weight, and a general formula

(Here, R represents an alkyl or alkenyl group having 12 to 22 carbon atoms, and m represents 0 or an integer of 1 to 10.)
A biodegradable resin composite material containing 0.1 to 5% by weight of an organic titanate represented by the formula: