JPH07122004B2 - Plastic modifier and manufacturing method thereof - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plastic modifier made of vegetable fibers and a method for producing the same, and more particularly to a master batch to be supplied when kneading vegetable fibers and a method for producing the same when reforming pellets for plastic molding. Regarding

[0002]

BACKGROUND OF THE INVENTION It is generally known to mix fibers with plastics for the purpose of modifying or increasing the amount of plastics. Recently, mixing with waste paper pulp has been considered due to ecological concerns. As a method of mixing fibers with plastics for the purpose of modifying or increasing the amount of plastics,
The conventional practice is to knead used dry and crushed waste paper into the softened plastic.

[0003]

SUMMARY OF THE INVENTION In the above prior art,
For example, when waste paper pulp is used as a raw material, there are the following problems except that the paper powder is simply used as a filler, and the industrial production technology is not established yet. (1) Since crushed waste paper is extremely bulky, its handling is extremely difficult, which is a decisive obstacle to productivity. (2) Sparks generated by contact between metal foreign objects such as staples, clips, rings, fasteners, etc., which are inevitable on used paper, and the crushing blade of the crusher are prone to the fire of crushed paper powder, which is a fire hazard. Is always big. (3) With dry pulverization, it is impossible to disintegrate waste paper into single fibers without damaging the fibers, and the fibers are cut in a bound state to form a powder, and the modifying effect as fibers is drastically reduced. (4) It is extremely difficult to efficiently separate and remove the metallic foreign matter crushed together with the waste paper from the dry raw material, and it is impossible to remove it industrially efficiently and reliably. (5) Even if the length of the fiber is preserved and the dry crushing is stopped in the form of paper pieces and kneaded with the resin, it takes a long time to further defibrate, and the fiber is absolutely dried at the melting temperature of the resin ( In the (dry) state, the fiber-to-fiber bonds are more strongly keratinized and become brittle, and the fibers become short fibers while undergoing thermal deterioration under the load of high temperature and high shear, and eventually paper powder similar to (3) above. Will turn into.

[0004]

[Means for Solving the Problems] The used paper is already made of paper,
The bond between fibers of hydrogenated paper is formed by hydrogen bond, and the bond is further strengthened by drying or dehydration. Therefore, as a means for separating and defibrating individual single fibers without giving mechanical damage to the fibers as much as possible, the waste paper is wetted with sufficient water to swell the fibers and to the minimum necessary amount. It must be defibrated by mechanical stirring. As described above, in the defibration of waste paper in a wet state, there is no danger of a fire due to sparks because the metallic foreign matter is in water even if it contacts the stirring blade during defibration. Furthermore, in the defibrated suspension of waste paper, metallic foreign substances settle due to the difference in specific gravity, separation due to centrifugal force, slits, and screening with a mesh (screw).
can be easily and surely separated and removed. In the disintegrated used paper suspension, the fibers are evenly dispersed and suspended, so multiple kinds of used paper can be mixed according to the purpose, and the addition of auxiliary agents and additives is minimal. Easily and uniformly with limited agitation. As described above, the present invention reversely utilizes water, which has been repelled in the field of synthetic resin and its processing technology, to improve the plastic modifier from a completely different papermaking technical idea that overturns common sense. Specifically, we tried to solve this problem as follows.

(1) A pulp raw material, such as waste paper, or a combination of a plurality of pulp raw materials is charged and separated with a pulper to obtain a water suspension. At this time, if the raw material is difficult to disintegrate
Since a stronger shearing force is required, it is necessary to use a kneader, but it is important to perform it in the presence of 60% or more of water. If the water content is less than 60%, the kinetic energy consumption is high, the disaggregation efficiency is poor, and there is even a risk of mechanical damage to the fiber due to too little water content. (2) The disaggregation raw material is diluted if necessary and is applied to a centrifuge cleaner (centrifuge) to remove heavy foreign matters. (3) Further coarse foreign matter is removed by screening. (4) The pulp suspension carefully selected by removing the dust of (2) and (3) does not allow strong fiber-to-fiber bonding again even when the pulp is dried, and is kneaded with the plastic molding pellets. At the time, an additive for promoting the dispersion of fibers is added and mixed.

The requirements for this additive are as follows: (1) Those that can sufficiently prevent hydrogen bonding between fibers when the fibers intervene in the fiber gap and dry. (2) When granulating pulp fibers into pellets, those that do not interfere with the molding. (3) When the completed pulp master is kneaded with a resin, it is possible to promote the uniform dispersion of individual single fibers in the resin in a short time due to the temperature conditions and shear stress. In addition, the amount of the additive added is such that plant fibers are present in the presence of 60% or more of water, fine particles having a particle size of 830 μm or less, and a fiber diameter of 50 μm.
At least one of fine fibers of m or less, liquid having a coating melting temperature or softening temperature of 200 ° C. or less, and a plasticizer having a boiling point of 200 ° C. or more or a cellulose hydrophobizing agent is added to the plant fiber in a total amount of 2 ~ 30 wt% is added.

In this case, when the fine particles are used as the additive, if the particle size is more than 830 μ, it is possible to intervene in the interstices between the fibers to obtain a sufficient distance to prevent hydrogen bonding between the fibers. The efficiency per addition amount becomes low,
If the added amount is increased, its quality influence cannot be ignored. The same can be said when using a fiber diameter exceeding 50 μ of fine fibers as an additive. When the softening temperature of the resin coating of the latex used as an additive exceeds 200 ° C., the fibers are not sufficiently dispersed unless the plant fibers are kneaded into the resin at a kneading temperature higher than that temperature. However, in consideration of heat deterioration during kneading of plant fibers, the upper limit temperature is generally 200 ° C., which is not practical. When the boiling point of the plasticizer used as an additive is lower than 200 ° C., for the same reason, the plasticizer boils at a kneading temperature of 200 ° C. or less, which is not practical. As mentioned above, if the addition amount of the additive specified for each is less than the lower limit, the binding of fibers will increase, and the nozzle will be clogged with the nozzle during injection molding, and molding will not be possible or the raw material will not be sufficiently supplied to the mold. Show
However, if the strength exceeds the upper limit, the various strengths were reduced by half and the material could not be used. Therefore, the range is empirically obtained.

As fine particles having a particle size of 830 μm or less, calcium carbonate, aluminum hydroxide, alumina, kaolin, silica, mica, zinc white, zinc white, titanium oxide, carbon black, and rouge are used as inorganic non-metals. . As the metal, iron powder, nickel powder, copper powder, and aluminum powder are used. As the organic resin, polyethylene, polypropylene, polystyrene, acrylic styrene, polyamide, polyester, epoxy, cellulose derivative is used. As the fine fibers having a fiber diameter of 50 μm or less, glass, carbon, rock wool, polyethylene, polypropylene, polyamide, polyester and cellulose derivatives are used. Two
As the liquid having a coating melting temperature or softening temperature of 00 ° C. or lower, a wax emulsion, a latex, a C ₁₈ or lower fatty acid or a metal salt thereof is used. Boiling point is 200 ℃
The above plasticizers or cellulose hydrophobizing agents are aromatic / aliphatic esters or alkyl ketene dimers (AK
D), alkenyl succinic anhydride (ASA), stearic anhydride, alkyl acid chloride, isocyanate, Z
An r complex compound and a Cr complex compound are used.

[0009]

The plant fiber is composed of cellulose fiber, and the cellulose fiber is a typical hydrophilic polymer substance. The hydrophilicity is due to the hydroxyl group of the cellulose molecule, and this hydroxyl group forms a hydrogen bond in the fiber and in the fiber gap. This hydrogen bond forms a bond represented as O-H because the H atom of each O-H group is attracted to the O atom of another adjacent O-H group, and also has a covalent bond element. Then, it is believed that a bond is formed by quantum mechanical resonance between two limit structures such as O-H ... O and O ... H-O. In the cellulosic fiber, this hydrogen bond is the OH of other cellulosic molecules in the fiber.
However, bonds can be formed similarly between OHs of adjacent fiber surfaces or OHs of adjacent water molecules.

Generally, in the cellulose fiber, intermolecular hydrogen bonds are formed in the crystal region within the fiber, and hydrogen bonds are formed through water molecules in the amorphous region of the crystal gap. Even in the gaps between the constituent units of fibers such as micelles, microfibrils, fibrils, lamellas, and single fibers, the OH of the cellulosic molecules on the surface of each constituent unit passes through the multi-molecular layer of water according to the hygroscopic state. Form a hydrogen bond. In the swollen state of the fiber, a larger amount of a multi-molecular layer of water intervenes in the gaps between the constituent units to be bonded, so that the fiber has flexibility in movement and becomes flexible. On the contrary, in the dry state, the intervening water is lost and the structural unit gap is narrowed, so that the freedom of movement is lost and the structure becomes rigid. When exposed to stronger dehydration conditions, one molecule of H ₂ O is dehydrated from two adjacent OHs to form -O-.
May form tel bonds. The ether bond is a stronger bond than the hydrogen bond, and the bond is no longer relaxed by the invasion of water molecules and completes an irreversible and firm bond. In this case, while the single fiber itself obtains high tensile strength, it loses more freedom and becomes brittle.

In the papermaking process, the fiber-to-fiber bonds mainly composed of hydrogen bonds have been completed, which are used to develop the product strength in the manufacturing process. Therefore, as described above, the hydrogen bond is further strengthened by drying and dehydration, but on the other hand, it absorbs and wets to form a multi-molecular layer of water in the interstices of the fiber to easily relax the bonding force. The kneaded state with the resin in the prior art is such that used paper, which is a synthetic paper, must be dried and dehydrated. The hydrogen bond loses the intervening water and the bond between the fibers becomes stronger. Since the melting and softening temperatures of the resin to be kneaded generally exceed 100 ° C., it may be a dehydration condition. In this condition, from the hydrogen bond of OH of fiber,
Further strengthening and forming an ether bond having a low degree of freedom. As a result, the binding of the fibers is hard and brittle, and if the binding of the fibers is attempted to be released by force, the fibers undergoing thermal deterioration will be fragile and unavoidably crushed.

Contrary to this, the present invention firstly uses the water repelled by the prior art sufficiently to loosen the inter-fiber bond based on the above-mentioned action, and at the minimum necessary amount of water that does not give mechanical damage to the fiber. It is premised on "completely disperse into single fiber" by mechanical shearing force, and then it does not form hydrogen bond again in the drying process until it becomes a finished product, and when it is kneaded with the resin, It provides a method to "disperse easily as single fibers". In order to prevent the defibrated waste paper fibers from forming a bond due to hydrogen bonds again in the subsequent drying process, in principle, the OH groups on the surface of each fiber must be blocked, and the cross-linking reaction of the hydrophobic group chemically occurs. Various additives are selected according to the purpose, such as the molecular level, the colloidal particle level physically formed by emulsion, and the powder particle level such as filler and pigment. In both cases, it is essential that the active OH is effectively chemically or physically blocked for the inter-fiber bonds on the fiber surface, and stable intercalation between the cellulose OH groups is possible. It is limited to those that promote the dispersion of the fibers in the resin and do not hinder the molding when compression granulating into pellets.

Specifically, in the present invention as satisfying this prerequisite, the additives are roughly classified into those having a physical action and those having a chemical action, and they are used as the former fine particles, that is, "dots", A physical fiber that is used as a fine fiber, that is, as a one-dimensional "line", as a coating, that is, as a two-dimensional "plane", and as a liquid, that is, as a three-dimensional "three-dimensional", and that seals the active surface of the fiber The method and the chemical method that directly and effectively reacts with OH are specified.
The principle is to physically and chemically fix OH groups which are difficult to hydrogen bond with each other, thereby making a distance between OH groups. With this distance, this hydrogen bond can be prevented even if there is no intervening substance such as an additive, that is, if there is a void. In fact, paper dust or cotton-like fibers can be dispersed in the resin relatively easily without the use of the abovementioned additives. However, because it is extremely bulky and light, it is not only difficult to handle, but it cannot be easily mixed into the viscous resin during kneading, and in order to knead the predetermined amount, it is forcedly pushed in several times. Or, there is no choice but to knead it over time. As a result, a time lag between the beginning and the end of the preparation is more or less unavoidable, and a difference in the heat history of the fibers is generated, and variations in product quality cannot be avoided.

Therefore, it is important for the present invention to specify that the fibers have a pellet-like or lump-like form having a major axis of 30 mm or less as a countermeasure. The reason why the major axis is limited to 30 mm or less is that the kneading takes a relatively long time when the major axis is exceeded. Further, it is empirically obtained that a bridge is likely to be formed in the hopper, which causes problems such as deterioration of weighing accuracy. The plastic modifier of the present invention is characterized in that it is disintegrated into a suspended state when stirred again in water. This re-disintegration property is convenient because it is possible to easily change the formulation or remake it without damaging the fiber, so that the raw material is not wasted. The fiber modifier thus obtained can exert its modifying effect as the fiber length of the raw material without the fiber being damaged and shortening due to the kneading with the resin of the conventional method. .

[0015]

Example 1 Waste newspaper of an amount corresponding to a pulp concentration of 3% (water content of 97%) was put into a pulper and was sufficiently separated. To the disintegrated pulp slurry, a cationic higher fatty acid emulsion containing 3 wt% of pulp and 10 wt% of carbon black (average particle size 0.1
μ) was added and mixed uniformly. Dust was removed from this blended raw material through a high-concentration cleaner and a Ramo-screen, and then the water content was adjusted to 20 to 25% through a two-stage dewatering process with a graded extractor and a screw press. This is a Fuji Paudal desk peretta-F-60N type with a diameter of 5 m.
Granulated into pellets of m and 5 mm in length.

Example 2 The step waste (waste ball waste paper) was disintegrated in the same manner as in Example 1, and 10 to 15 μm of polyethylene fine powder was added to the pulp slurry in an amount of 5 wt% with respect to the pulp. Amphoteric latex (melting point is about 150 ° C) as a fixing agent for 3 wt% of pulp
% Was added and thoroughly mixed with stirring. This blended raw material was subjected to dust removal and granulation in the same manner as in Example 1 to form pellets having a diameter of 5 mm.

Example 3 The deinked pulp of high-quality waste paper was disintegrated and disintegrated in the same manner as in Example 1, and the pulp slurry was defibrated with 2% by weight of alkenyl succinic anhydride (ASA) and an average particle size of 0. 5 μl of talc (10 wt%) was added, and the mixture was uniformly mixed, and then, as in Example 1, dust removal, dehydration, and water content adjustment were performed before granulation. The pellet had a diameter of 5 mm and a length of 5 mm.

Example 1.2.3. With 50 parts of polypropylene. Fifty parts of the pellets obtained in 1 above were kneaded with an MS type pressure kneader DS55-100 type manufactured by Moriyama Seisakusho Co., Ltd. and injection-molded to obtain test pieces to obtain the data shown in Table 1 below. The conventional method sample used for comparison is said to have the highest efficiency in dry pulverization.
l: Newspaper waste paper was crushed with Tarbomill (manufactured by Tarbo Kogyo Co., Ltd.), and pellets obtained by kneading with PP with an MS type pressure kneader as described above were injection-molded into a test piece for testing. did.

The modifying material of the present invention was pelletized and charged in a predetermined amount at one time, whereas the crushed waste paper of the conventional example is light and bulky, so that it is difficult to measure the predetermined amount. ,
Moreover, it was not possible to do it all at once, and it was necessary to repeat the pressurization to do so, and to do the work several times. Therefore, the kneading time inevitably took longer than necessary, and the kneading time of 2 to 3 times had to be extended. Therefore, the conventional example has significantly different conditions at the beginning and the end of preparation,
I was still worried about quality assurance.

As shown in the data in Table 1 below, it is apparent that the examples according to the present invention are superior in almost all physical properties as compared with the PP of the base resin as well as that of the conventional method. Even if the kneading of waste paper pulverized by the conventional method, Tabomill, is continued for several tens of minutes, spots of unsatisfactorily dispersed binding fibers remain and finally a foul odor is generated. On the other hand, according to the present invention, since uniform dispersion is completed by kneading for several minutes,
The mechanical and thermal load on the fibers can be kept to a minimum.

[0021]

[Table 1]

A comparative example in the case where the addition amount of each additive exceeds the specified range is shown in Table 2 below.

[Table 2] The plastic products modified according to the present invention as shown in the above table had a combustion calorie of 6000 to 6500 cal / g, which was significantly lower than that of the raw plastic.

[0023]

As can be seen from the above description, the plastic modifier according to the present invention is a fine particle having a particle size of 830 μm or less,
Fine fibers with a fiber diameter of 50 μm or less, film melting at 200 ° C or less
Liquid with melting or softening temperature, boiling point 200 ° C
Less of the above plasticizers or cellulose hydrophobizing agents
2 to 30% by weight of one additive with respect to the plant fiber
Since the pellets or agglomerates of the contained plant fibers are formed to have a major axis of 30 mm or less, there is no mechanical damage to the plant fibers themselves, and before the plastic kneading, the above-mentioned additives prevent the inter-vegetable fiber bonds and the plastic kneading. Time is sticky
Pellets or lumps with a major axis of 30 mm or less in a thick resin
The fibers in the shape of
In addition, the plant fibers are uniformly dispersed by the above additives, and various physical properties of the plastic such as tensile strength, bending strength, bending elasticity, and heat distortion temperature can be improved.

Further, the plastic modifier of the present invention can be disintegrated into a suspended state by stirring again in water. As a result, this re-disintegration property causes damage to the fiber when the formulation is changed or remade. It can be done easily without any waste, and there is the convenience that raw materials can be used effectively without waste.
Furthermore, the method for producing a plastic modifier according to the present invention is characterized in that plant fibers are added in the presence of 60% or more of water in a particle size of 830
Fine particles of less than μm, fine fibers of 50 μm or less in diameter,
At least one kind of liquid material having a coating melting temperature or softening temperature of 00 ° C or lower, a plasticizer having a boiling point of 200 ° C or higher or a cellulose hydrophobizing agent is added in a total amount of 2 to 30% by weight based on the plant fiber. Since it is dispersed in single fibers, dust-removed, mixed, then dehydrated and granulated, it is easy to remove metallic foreign substances even when disintegrating using waste paper, etc. Etc., less consumption of power energy, good defibration efficiency, and smooth and rapid uniform dispersion of fibers in the resin even when kneading the resin and the granular material made of plant fibers. it can.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display area // B29K 1:00

Claims (5)

[Claims] 1. Fine particles having a particle diameter of 830 μm or less, and a fiber diameter of 5.
Fine fibers of 0 μm or less, coating melting temperature of 200 ° C. or less
Or a liquid with a softening temperature, a boiling point of 200 ° C or higher
At least one of a plasticizer or a cellulose hydrophobizing agent
30 to 30% by weight of pellets or agglomerates of plant fibers containing 2 to 30% by weight of additives of the class 3 to plant fibers.
A plastic modifier characterized by being less than or equal to mm. 2. Fine particles having a particle size of 830 μm or less are calcium carbonate, aluminum hydroxide, alumina, kaolin, silica, mica, zinc white, zinc white, titanium oxide, carbon black, rouge, and iron for metals as inorganic non-metals. Powder, nickel powder, copper powder, aluminum powder, organic resin is polyethylene, polypropylene, polystyrene, acrylic styrene, polyamide, polyester, epoxy, cellulose derivative, and the fine fibers having a fiber diameter of 50 μm or less are
Liquid substances that are glass, carbon, rock wool, polyethylene, polypropylene, polyamide, polyester, and cellulose derivatives, and have a film melting temperature or softening temperature of 200 ° C. or less are wax emulsion, latex, C ₁₈ or less fatty acid or metal salt thereof. And the plasticizer or cellulose hydrophobizing agent having a boiling point of 200 ° C. or higher is
Aromatic / aliphatic ester or alkyl ketene dimer (AKD), alkenyl succinic anhydride (ASA), stearic anhydride, alkyl / acid chloride, isocyanate, Zr complex compound, Cr complex compound. 1. The plastic modifier according to 1 . Wherein it is possible disaggregation, dispersed in water, according to claim 1 or 2 plastic reforming material, wherein that the granules of the pellet or lump consisting vegetable fibers. 4. Plant fibers in the presence of 60% or more water,
At least one of fine particles having a particle diameter of 830 μm or less, fine fibers having a fiber diameter of 50 μm or less, a liquid substance having a film melting temperature or a softening temperature of 200 ° C. or less, a plasticizer having a boiling point of 200 ° C. or more, or a cellulose hydrophobizing agent. A method for producing a plastic modifier, which comprises adding 2 to 30% by weight to plant fibers in total, dispersing into single fibers, removing dust, mixing, then dehydrating and granulating. 5. Fine particles with a particle size of 830 μm or less are calcium carbonate, aluminum hydroxide, alumina, kaolin, silica, mica, zinc white, zinc white, titanium oxide, carbon black, rouge, and iron for metals as inorganic non-metals. Powder, nickel powder, copper powder, aluminum powder, organic resin is polyethylene, polypropylene, polystyrene, acrylic styrene, polyamide, polyester, epoxy, cellulose derivative, and the fine fibers having a fiber diameter of 50 μm or less are
Liquid substances that are glass, carbon, rock wool, polyethylene, polypropylene, polyamide, polyester, and cellulose derivatives, and have a film melting temperature or softening temperature of 200 ° C. or less are wax emulsion, latex, C ₁₈ or less fatty acid or metal salt thereof. And the plasticizer or cellulose hydrophobizing agent having a boiling point of 200 ° C. or higher is
Aromatic / aliphatic ester or alkyl ketene dimer (AKD), alkenyl succinic anhydride (ASA), stearic anhydride, alkyl / acid chloride, isocyanate, Zr complex compound, Cr complex compound. 4. The method for producing a plastic modifier according to 4 .