JP5124320B2 - Paper-containing resin composition, method for producing the same, and molded product obtained therefrom - Google Patents

Description

  The present invention relates to a paper-containing resin composition obtained by pulverizing fine paper, laminated paper cutting scraps, recovered high-quality paper or laminated paper waste paper, or a mixture thereof and mixing with a resin raw material. More specifically, by improving the kneadability between the coarsely pulverized paper and the resin raw material, the undispersed paper is eliminated and uniformly mixed and dispersed, resulting in the fluidity of the paper-containing resin composition. It is related with the paper containing polyolefin-type resin composition which can increase the content rate of paper by improving.

  Conventionally, for the purpose of improving the moldability of the kneaded material of wood-based material and resin, the wood-based material is refined by applying mechanical and chemical treatment to paper, and the resin is selected according to the molding application. A method of kneading with a resin is employed. As an example of this mechanical / chemical treatment, there is a method in which a wood-based material pulverized to a predetermined particle size is esterified with a polybasic acid anhydride or the like to make it finer, thereby improving the kneadability with a resin (for example, Patent Document 1). Or see 2).

Japanese Patent No. 36551117 Japanese Patent No. 3933315

  However, with regard to paper, there are no examples of the mechanical and chemical treatments described above. If only the mechanical treatment is used and the content of the paper exceeds a certain range, the thermal fluidity during the molding process may decrease. There was a problem that the mechanical strength of the molded product was lowered.

  The first object of the present invention is to provide a kneaded composition for producing a molding composition by kneading a crushed or pulverized paper material and a thermoplastic resin without reducing the mechanical strength of the molded product. It is to improve hot melt fluidity. In other words, improving the kneadability of coarsely pulverized products and resin raw materials without reducing the pulverized particle size of fine paper, laminated paper cutting scraps, recovered fine paper or laminated paper waste paper, or a mixture of these By eliminating the undispersed material of the paper and mixing and dispersing uniformly, as a result, by improving the fluidity of the paper-containing resin composition, moldability such as injection molding even if the paper content is increased Is to provide a good paper-containing resin composition. Another object is to increase the content of the paper material excluding the filler by increasing the paper content.

  The second object of the present invention is to use a paper-containing resin composition according to the present invention, a paper-containing resin molded article having high paper content, no discoloration and odor, low water absorption, and excellent impact strength. Is to provide.

  The third object of the present invention is to provide a production method for obtaining a paper-containing resin composition that is uniformly mixed and dispersed without kneading paper by kneading using a twin-screw extruder. It is in.

  The present inventors diligently investigated the relationship between the composition of the paper used for the pulverized paper and the pulverized product, and the relationship between the workability when the resin was mixed and the quality of the paper-containing resin composition. As a result, the inventors have found that the above objects can be achieved at the same time, and have reached the present invention.

The paper-containing resin composition according to the present invention comprises a pulverized paper esterified with a polybasic acid anhydride, a polyolefin resin, and at least a magnesium compound and titanium oxide as an alkaline earth metal compound. the polyolefin resin Ri principal component der content of the pulverized material is 50 to 70 wt%, the content of the polyolefin-based resin is 15 to 48 wt%, the content of the magnesium compound, It is 0.1-5 mass% with respect to the total mass in terms of magnesium oxide, and the content of the titanium oxide is 2-15 mass% with respect to the paper material . By neutralizing the organic acid with the magnesium compound, discoloration and generation of odor can be suppressed. Titanium oxide improves the fluidity of the paper-containing resin composition and improves the mechanical strength.

  The paper-containing resin composition according to the present invention includes a case where the polyolefin resin is a polypropylene resin alone or a mixture of a polypropylene resin and a polyethylene resin.

  In the paper-containing resin composition according to the present invention, the polybasic acid anhydride is maleic anhydride, and the proportion of maleic anhydride introduced by esterification is 0.1 to 5% by mass with respect to the paper material. It is preferable that The fluidity of the paper-containing resin composition is improved and the water absorption rate is reduced. There is no undispersed paper and it is easy to mix and disperse uniformly.

  In the paper-containing resin composition according to the present invention, the paper is preferably a paper containing 70% by mass or more of exposed kraft pulp. High-quality paper, cut waste of laminated paper, recovered high-quality paper or used paper of laminated paper, or a mixture thereof. By containing a large amount of bleached kraft pulp, the strength of the paper-containing resin composition is increased.

  In the paper-containing resin composition according to the present invention, the content of the pulverized paper material (excluding filler) is preferably 51% by mass or more. That is, it can be set as an environment-friendly paper-containing resin composition.

The method for producing a paper-containing resin molded product according to the present invention comprises a step of pulverizing a paper containing 70% by mass or more of bleached kraft pulp to obtain a pulverized paper product, and the pulverized paper product is a polybasic acid anhydride. A step of esterification, a step of kneading a magnesium compound and titanium oxide as esterified paper pulverized product, polyolefin resin, and alkaline earth metal compound, and neutralizing an organic acid with the alkaline earth metal compound; , and kneaded with the resulting kneaded product further twin screw extruder possess obtaining a paper-containing resin composition, and the content of the titanium oxide, and 2 to 15 wt% with respect to the paper stock It is characterized by that.

  In the method for producing a paper-containing resin molded product according to the present invention, it is preferable that the pulverized particle size of the pulverized paper is 0.5 to 2.5 mm. Good kneadability is obtained, and pulverization is easy and long run operation is possible.

  The paper-containing resin molded product according to the present invention is characterized by being formed of the paper-containing resin composition of the present invention.

  By the paper-containing resin composition of the present invention, fine paper cutting scraps containing 70% by mass or more of ground kraft pulp that has been crushed or pulverized or recovered old paper and / or bleached kraft pulp of 70% by mass or more Thermal melt flow of kneaded composition when kneading scraps of polyethylene film laminated paper based on contained base paper and / or recovered waste paper of polyethylene film laminated paper and thermoplastic resin to form molding composition Can be improved. That is, the paper-containing resin composition of the present invention eliminates undispersed paper by improving the kneadability between the coarsely pulverized product and the resin raw material without reducing the pulverized particle size of the paper. Thus, even if the content of the laminated paper is increased by improving the fluidity of the paper-containing resin composition, the moldability such as injection molding is good.

  The paper-containing resin molded article of the present invention uses the paper-containing resin composition according to the present invention to cut high-quality paper containing 70% by mass or more of crushed or pulverized bleached kraft pulp or recovered fine quality It is possible to increase the content of cutting waste of polyethylene film laminated paper and / or recovered recovered paper of the polyethylene film laminated paper based on base paper containing 70% by weight or more of waste paper and / or bleached kraft pulp, and There is no discoloration or odor and excellent impact strength.

  In the method for producing the paper-containing resin composition of the present invention, a reaction with a polybasic acid anhydride and an alkaline earth metal compound, and the promotion of refinement by the mechanical action of titanium oxide, and a twin screw extruder were used. By kneading, it is possible to obtain a paper-containing resin composition having good fluidity, in which paper is not dispersed and is uniformly mixed and dispersed.

  Hereinafter, although an embodiment is shown and explained in detail about the present invention, the present invention is limited to these descriptions and is not interpreted. In addition, the embodiment may be modified as long as the effects of the invention are achieved.

  The paper-containing resin composition according to the present embodiment contains at least a pulverized paper esterified with a polybasic acid anhydride, a polyolefin resin, an alkaline earth metal compound, and titanium oxide, and the pulverized product and the polyolefin. Resin is the main component. The paper is preferably paper containing 70% by mass or more of bleached kraft pulp. In addition, when the paper containing bleached kraft pulp and medium quality paper such as TMP (thermomechanical pulp) and GP (ground pulp) are combined, the paper as a whole contains 70% by weight or more of bleached kraft pulp Is also included. The paper may be a laminated paper based on a base paper containing softwood bleached kraft pulp, or a combination of the laminated paper and the base paper before lamination.

  High-quality paper is paper made only from bleached kraft pulp, and is used for printing paper, writing paper, and the like. A typical example is a copy paper called a so-called PPC paper, which is a print paper in which a white pigment is not applied to the paper surface. Further, the scraps of the used copy and recovered waste paper may be used. Increases the efficiency of effective use of resources. The pulp constituting the base paper of the fine paper is mainly hardwood bleached kraft pulp (LBKP), and the blending ratio of LBKP in the base paper is at least 70% by mass or more. More preferably, it is 80 mass% or more. When the blending ratio is less than 70% by mass of LBKP, the strength suitability of the paper-containing resin composition of the present embodiment tends to be insufficient.

The laminated paper has a polyethylene resin having a film thickness of 20 to 50 μm laminated on one side or both sides of the base paper. Here, the laminated paper is laminated paper for liquid containers, laminated paper cutting waste or laminated paper recovered waste paper used individually, combined use of laminated paper and laminated paper cutting waste, laminated paper and laminated paper recovered Use of a combination of waste paper, use of laminated paper cutting waste and laminated paper recovered waste paper combination, or use of a combination of laminated paper and laminated paper cutting waste and laminated paper recovered paper preferable. Increases the efficiency of effective use of resources. A typical example is a laminated paper for a liquid container called a so-called milk carton, or printing cut waste (hereinafter referred to as “print trimming waste”), or recovered paper such as a milk pack (hereinafter referred to as “milk trimming waste”). These are collectively called “laminated waste paper”.) The base paper preferably has a basis weight of 300 to 500 g / m ² , a paper thickness of 0.4 to 0.6 mm, and a density of 0.7 to 0.6 g / cm ³ . The pulp constituting the base paper of the laminated paper is mainly softwood bleached kraft pulp (NBKP), and the blending ratio of NBKP in the base paper is at least 70% by mass or more. More preferably, it is 80 mass% or more. If the NBKP content is less than 70% by mass, the strength suitability of the paper-containing resin composition of the present embodiment tends to be insufficient. As a material of the laminated film, for example, a low density polyethylene resin or a high density polyethylene resin is used.

  A pulverized paper product is obtained by pulverizing paper containing 70% by weight or more of exposed kraft pulp. The pulverized particle size of the pulverized product is preferably 0.5 to 2.5 mm, although it is affected by the subsequent kneading conditions. More preferably, it is 1.0-2.0 mm. The particle size of the pulverized paper is defined by the diameter of the screen obtained by passing through a predetermined screen (hereinafter simply referred to as “particle size”). In order to improve the kneadability with the resin, the finer the particle size of the paper, the better. By setting the pulverized particle size to 2.5 mm or less, good kneadability is easily obtained. Regarding the operation of the pulverizer, the finer the pulverized particle size, the more likely the screen or flat screen is clogged, and the more likely the problem of contact between the fixed blade and the rotary blade due to the temperature rise inside the pulverizer. When crushing laminated paper laminated with heat-meltable resin such as polyethylene, the smaller the pulverized particle size, the more likely the clogging of the screen or flat net due to heat melting of the resin will occur, and the temperature inside the crusher will rise. Problems such as contact between the fixed blade and the rotary blade due to the above are likely to occur. According to the experiments by the present inventors, particularly when pulverizing to a particle size of less than 0.5 mm, the operation of the pulverizer becomes extremely difficult. However, when the particle diameter is 0.5 mm or more, long run operation is possible with almost no trouble of this kind, and the grinding efficiency is improved.

  In the paper-containing resin composition according to this embodiment, a pulverized product and a polyolefin-based resin are main components, and the total content thereof is preferably 85 to 98 mass%, more preferably 90 to 95 mass%. It is. If it is less than 85% by mass, the fluidity and dispersibility may be inferior, and if it exceeds 98% by mass, the color change may be noticeable. Here, the content of the pulverized product is preferably 50 to 70% by mass, more preferably 55 to 60% by mass. When the amount is less than 50% by mass, the amount of pulverized material mixed is reduced, resulting in poor recycling efficiency. When the amount exceeds 70% by mass, fluidity and dispersibility may be inferior. Moreover, it is preferable that content of polyolefin resin shall be 15-48 mass%, More preferably, it is 25-43 mass%. If the amount is less than 15% by mass, the strength may decrease. If the amount exceeds 48% by mass, the amount of pulverized material mixed in decreases, resulting in poor recycling efficiency. Furthermore, the polyolefin resin includes a polypropylene resin, a polyethylene resin, a polybutene resin, a methylpentene resin, and the like, more preferably a polypropylene resin alone or a mixture of a polypropylene resin and a polyethylene resin, which is compatible with paper. That's fine.

  The polybasic acid anhydride used in the present embodiment includes, for example, maleic anhydride, phthalic anhydride, or succinic anhydride, and is selectively added to the pulverized paper before kneading with the resin. By esterifying cellulose and hemicellulose in the inside, it is effective in improving the fluidity of a pulverized product having a coarse particle size without reducing the pulverized particle size of paper. Among these, maleic anhydride is more preferable, and the addition amount is selected in the range of 0.1 to 5% by mass with respect to the paper material. More preferably, it is 0.5-3 mass%. If this amount is less than 0.1% by mass, the effect of improving the fluidity may be insufficient, and if it exceeds 5% by mass, the physical properties of the paper-containing resin composition and the paper-containing resin molded product may be deteriorated.

The alkaline earth metal compound used in the present embodiment includes, for example, magnesium oxide, calcium oxide, zinc oxide and the like, added when kneading with a resin, and after reacting with moisture in the pulp and changing to a hydroxide, By neutralizing the polybasic acid remaining after esterification and / or the organic acid generated by thermal decomposition of the pulp, it is effective to prevent the generation of odor and gas. Among these, magnesium oxide is more preferable, and the addition amount is selected in the range of 0.1 to 5% by mass with respect to the paper material according to the present embodiment. More preferably, it is 0.5-3 mass%. If this amount is less than 0.1% by mass, the neutralization effect may be insufficient. If it exceeds 5% by mass, the physical properties of the paper-containing resin composition and the paper-containing resin molded product may be reduced, and the economy may be reduced. Is not preferable. When the paper-containing resin composition is formed, for example, when magnesium oxide is added, the magnesium oxide becomes a magnesium compound by the neutralization reaction. Therefore, the magnesium oxide content is measured from the state of the paper-containing resin composition. Sometimes it is calculated in terms of magnesium oxide.

Titanium oxide used in the present embodiment is added as an inorganic filler component when kneaded with a resin, but is effective as a white pigment, and at the same time, the refinement of pulp fibers is promoted by the mechanical action during kneading. Improving the fluidity of the paper-containing composition. In the paper-containing composition according to the present invention, the content of titanium oxide is preferably 2 to 15% by mass with respect to the paper material. 3-10 mass% is more preferable. When the content of titanium oxide is less than 2% by mass, the effect of improving the fluidity is insufficient, and when it exceeds 15 % by mass, the fluidity is decreased. Further, calcium carbonate as an inorganic filler component is not effective as a white pigment or for improving fluidity.

  In the paper-containing resin composition of the present embodiment, components other than the pulverized paper and resin may be included as necessary. For example, a fluidity improver may be added.

The addition of the fluidity improver used in the present embodiment is either when blended when kneaded the pulverized paper pulverized product and the resin, or when blended when molding the paper-containing resin composition But you can. By containing a fluidity improver, heat generation during molding is prevented, and moldability during molding is improved. In addition, when mix | blending a fluidity improver at the time of kneading | mixing, not only the effect at the time of shaping | molding but the effect which prevents the heat_generation | fever by friction at the time of kneading | mixing is also acquired. The fluidity improver is not particularly limited as long as it prevents heat generation due to friction during molding and improves the fluidity of the paper-containing resin composition. For example, polyethylene wax, low density polyethylene, stearic acid, stearic acid Examples include higher fatty acids such as zinc and calcium stearate or salts thereof, and various higher fatty acid esters. The melting point of the fluidity improver is preferably 100 ° C. or lower, and examples thereof include fatty acid amides such as erucic acid amide, oleic acid amide, and stearic acid amide. One kind of these may be used, or two or more kinds may be used in combination.

  Moreover, you may add auxiliary agents, such as a compatibilizing agent, resin antioxidant, and an antistatic agent, as needed, in the range which does not affect the effect of this invention.

  In the paper-containing resin composition according to this embodiment, the total amount of paper materials excluding the filler is preferably 51% by mass or more. It can be set as an environment-friendly paper-containing resin composition. More preferably, it is 51-70 mass%. Components other than the paper material in the paper-containing resin composition are mainly composed of a resin. The pulverized paper contains all the constituents. For example, in the case of LBKP, pulp other than LBKP, resin content in base paper, and laminated paper, a laminated film is included.

  The paper-containing resin composition of the present embodiment is preferably kneaded with a twin-screw extruder, and at this time, the amount of undispersed material is reduced and is easily homogenized. The treatment with a twin screw extruder is preferable because it can be more homogeneous twice or more than once. At this time, it is more preferable to knead | mix at the temperature of 100-200 degreeC. Before kneading with a twin-screw extruder, the paper pulverized product and resin weighed to a predetermined ratio and an auxiliary agent such as a fluidity improver to be added as necessary are preliminarily mixed with a mixer such as a Henschel mixer. It is preferable to mix uniformly. The fibers are defibrated and cut by the flow and kneading action of the screw of the twin screw extruder, and the dispersibility and fluidity of the paper-containing resin composition are improved.

  The paper-containing resin composition according to the present embodiment preferably has an MFR (test temperature = 190 ° C., test load = 10 kg) specified by ASTM D1238-04c of 2.0 to 55.0 g / 10 min. The paper-containing resin composition in which the MFR falls within this range has a sufficiently uniform dispersion of the paper pulverized product and the resin even though it contains a pulverized paper product containing 70% by weight or more of bleached kraft pulp. Yes. When the MFR is less than 2.0 g / 10 min, dispersion of the pulverized paper and the resin is insufficient. Further, in the present embodiment containing a large amount of LBKP, when the pulverized paper and the resin are sufficiently dispersed, the MFR approaches 55.0 g / 10 min. The value of this MFR is not greatly affected by the presence or absence of the addition of a fluidity improver when kneading with a twin screw extruder. Moreover, it is preferable that the water absorptivity measured according to JIS K 7209: 2000 "Plastics-Determination of water absorptivity" D method is less than 0.10. The tensile strength measured according to JIS K 7113: 1995 “Plastic Tensile Test Method” is preferably 33 MPa or more. Furthermore, it is preferable that the bending strength measured according to JIS K 7203: 1995 “Bending test method of hard plastic” is 63 MPa or more.

  Thus, the paper-containing resin composition according to the present embodiment includes a step of pulverizing paper containing 70% by mass or more of bleached kraft pulp to obtain a pulverized paper product, and the pulverized paper product is a polybasic acid anhydride. And a step of kneading the esterified pulverized paper, polyolefin resin, alkaline earth metal compound and titanium oxide, and neutralizing the organic acid with the alkaline earth metal compound. A kneaded product is further kneaded with a twin screw extruder to obtain a paper-containing resin composition. The base paper before lamination may be added to the laminated paper.

  Next, the paper-containing resin molded product according to this embodiment is obtained by molding the paper-containing resin composition according to this embodiment with an injection molding machine. The paper-containing resin molded product according to the present embodiment has a melt mass flow rate (MFR) (test temperature = 190 ° C., test load = 10 kg) defined by ASTM D1238-04c of 2.0 to 55.0 g / 10 min. Is preferred. Here, it is preferable to add a fluidity improver in the step of obtaining the paper-containing resin composition and / or the step of obtaining the paper-containing resin molded product.

  The paper-containing resin molded article according to the present embodiment thus obtained contains at least a pulverized paper esterified with a polybasic acid anhydride, a polyolefin resin and an alkaline earth metal compound, and titanium oxide. The pulverized product and polyolefin resin are the main components. Here, the melt mass flow rate (MFR) (test temperature = 190 ° C., test load = 10 kg) defined by ASTM D1238-04c is preferably 2.0 to 55.0 g / 10 min. The paper preferably contains 50% by mass or more of NBKP. The MFR value of the paper-containing resin composition and the MFR value after making the paper-containing resin molded product are substantially the same. This paper-containing resin molded product is free from discoloration and odor and has excellent impact strength.

  In the paper-containing resin molded product of the present embodiment, the contained high-quality paper is high-quality paper cutting waste such as PPC paper or recovered high-quality paper waste paper, or polyethylene film laminated paper cutting waste or recovered waste paper Effective utilization of resources. Moreover, it is preferable that the total amount of the paper raw material excluding the filler in the paper-containing resin molded product is 51% by mass or more, which is an environment-friendly type. Examples of the paper-containing resin molded product include a dish, a cup, a bowl, a spoon, and a comb.

  EXAMPLES Next, although an Example is given and this invention is demonstrated more concretely, this invention is not limited to these Examples. Further, “%” and “part” in the examples indicate “% by mass” and “part by mass” unless otherwise specified.

Example 1
[Manufacture of A and B of crushed paper]
A. Contains 95% by weight of LBKP, basis weight 69 g / m ² , thickness 92 μm, density 0.75 g
/ Cm ³ Paper milling process for high quality PPC paper scraps (model BO-25)
75 and HaA-2542: manufactured by Horai Co., Ltd.) and passed through a 0.5 mmφ screen to obtain a pulverized paper product.
B. The base paper of the polyethylene film laminated paper contains 90% by mass of NBKP, grinds the milk carton printing trimming waste having a basis weight of 393 g / m ² , a thickness of 0.48 mm and a density of 0.82 g / cm ³ (model BO-2575). And HaA-2542 (manufactured by Horai) and passed through a 0.5 mmφ screen to obtain a pulverized polyethylene film laminated paper.
[Production of paper-containing resin composition]
Next, for each of A and B, maleic anhydride (trade name: maleic anhydride: manufactured by NOF Corporation) was added in an amount of 0.5% by mass based on the pre-dried paper pulverized product, and esterified. Advanced. Next, titanium oxide (trade name Typaque A-220: manufactured by Ishihara Sangyo Co., Ltd.) is added to the esterified pulverized product in an amount of 8.0% by mass with respect to the pulverized paper product, and a modified polypropylene resin (trade name Umex 1010). : Sannopco) is added in an amount of 0.5% by mass with respect to the pulverized paper, and polypropylene resin (trade name J-5051HP: Idemitsu Petrochemical Co., Ltd.) is added to 30% by mass with respect to the pulverized paper. Add magnesium oxide as a neutralizing agent (trade name: Magnesium oxide: manufactured by Tomita Pharmaceutical Co., Ltd.) in an amount of 0.5% by mass with respect to the total mass, mix evenly with a Henschel mixer, and then use a desk pelleter. (Model F-60: manufactured by Fuji Powder Co., Ltd.) and a twin screw extruder were pelletized to obtain a paper-containing resin composition. The paper ratio in this paper-containing resin composition was 55% by mass.
[Manufacture of injection molded products for evaluation]
From the paper-containing resin composition, an injection-molded product for evaluation was prepared using an injection molding machine (model J35ELII: manufactured by Nippon Steel Works) with a cylinder set temperature of 180 ° C. Here, the paper pulverized product A is used as Example 1A, and the paper pulverized product B is used as Example 1B.

(Example 2A)
In the manufacture of the paper pulverized product A in Example 1, the screen was changed from a 0.5 mmφ screen to a 1.0 mmφ screen, and maleic anhydride (trade name maleic anhydride: manufactured by NOF Corporation) was used as the pulverized paper product. On the other hand, the amount is changed from 0.5% by mass to 1.5% by mass, and the amount of titanium oxide (trade name Typaque A-220: manufactured by Ishihara Sangyo Co., Ltd.) is 6.0% by mass with respect to the pulverized paper. In addition, a paper-containing resin was used in the same manner except that magnesium oxide (trade name: magnesium oxide manufactured by Tomita Pharmaceutical Co., Ltd.) was changed from 0.5% by mass to 1.5% by mass with respect to the total mass as a neutralizing agent. A composition and an injection molded product for evaluation were obtained. The paper ratio in this paper-containing resin composition was 55% by mass.

(Example 2B)
In the manufacture of B of the pulverized paper of Example 1, the screen was changed from a 0.5 mmφ screen to a 1.0 mmφ screen, and maleic anhydride (trade name maleic anhydride: manufactured by NOF Corporation) was 0 The amount was changed from 5% by mass to 1.5% by mass, and titanium oxide (trade name Typaque A-220: manufactured by Ishihara Sangyo Co., Ltd.) was added in an amount of 6.0% by mass with respect to the pulverized paper. Paper-containing resin composition in the same manner except that magnesium oxide (trade name magnesium oxide: manufactured by Tomita Pharmaceutical Co., Ltd.) was changed from 0.5% by mass to 1.5% by mass with respect to the total mass as a neutralizing agent. And the injection-molded article for evaluation was obtained. The paper ratio in this paper-containing resin composition was 55% by mass.

(Example 3A)
In the production of the paper pulverized product of Example 2A, the base paper of the pulverized product was changed to a recovered copy paper containing 70% by weight of LBKP, a basis weight of 64 g / m ² , a thickness of 88 μm, and a density of 0.75 g / cm ^3. In addition, a paper-containing resin composition and an evaluation injection-molded product were obtained in the same manner except that titanium oxide (trade name: Typaque A-220: manufactured by Ishihara Sangyo Co., Ltd.) was changed to 10.0% by mass with respect to the pulverized paper. It was. The paper ratio in this paper-containing resin composition was 55% by mass.

(Example 3B)
In the production of the pulverized paper of Example 2B, the raw material of the pulverized material was from milk carton printing trimming waste, the base paper of the polyethylene film laminated paper contained 80% by mass of NBKP, the basis weight was 362 g / m ² , and the thickness was 0.00. The same method except for changing to a recovered milk pack of 47 mm and a density of 0.78 g / cm ³ and changing the titanium oxide (trade name Typaque A-220: manufactured by Ishihara Sangyo Co., Ltd.) to 12.0% by mass with respect to the pulverized paper. A paper-containing resin composition and an evaluation injection-molded product were obtained. The paper ratio in this paper-containing resin composition was 55% by mass.

(Example 4A)
In the production of the paper-containing resin composition of Example 3A, the blending amount of the paper pulverized product was changed from the amount that the paper ratio in the paper-containing resin composition was 55% by mass to the paper ratio in the paper-containing resin composition. In the production of the pulverized paper of Example 3A, the screen was changed from a 1.0 mmφ screen to a 2.0 mmφ screen, and maleic anhydride (trade name maleic anhydride: Nippon Oil & Fats was changed to 60% by mass. Was changed from 1.5% to 2.0% by weight based on the pulverized paper, and titanium oxide (trade name Typaque A-220, manufactured by Ishihara Sangyo Co., Ltd.) was changed to crushed paper. An amount of 3.0% by mass was added, and magnesium oxide (trade name: Magnesium oxide: manufactured by Tomita Pharmaceutical Co., Ltd.) as a neutralizing agent was changed from 1.5% to 2.0% by mass with respect to the total mass. Except for the paper-containing resin composition and the same method To obtain a value for the injection molded article.

(Example 4B)
In the production of the paper-containing resin composition of Example 3B, the blending amount of the paper pulverized product was changed from the amount that the paper ratio in the paper-containing resin composition was 55% by mass to the paper ratio in the paper-containing resin composition. In the production of the pulverized paper of Example 3B, the screen was changed from a 1.0 mmφ screen to a 2.0 mmφ screen in the production of the paper pulverized product of Example 3B. 2) to 1.5% by mass to 2.0% by mass with respect to the pulp component, and titanium oxide (trade name Typaque A-220: manufactured by Ishihara Sangyo Co., Ltd.) to the pulverized paper. Except for changing the amount to be 0% by mass and changing the magnesium oxide (trade name: Magnesium oxide: manufactured by Tomita Pharmaceutical Co., Ltd.) as a neutralizing agent from 1.5% by mass to 2.0% by mass with respect to the total mass. In the same manner, a paper-containing resin composition and To obtain a value for the injection molded article.

(Example 5A)
In the production of the injection-molded article for evaluation in the production of the paper-containing resin composition of Example 1A, titanium oxide (trade name: Typaque A-220: manufactured by Ishihara Sangyo Co., Ltd.) is 12.0% by mass with respect to the pulverized paper. The same method except that 0.5 part of erucic acid amide (trade name Alflow 10: manufactured by NOF Corporation) was added to 100 parts of the paper-containing resin composition as a fluidity improver. An injection molded product was obtained.

(Comparative Example 1A)
In the manufacture of the pulverized paper of Example 1A, the screen was changed from a 0.5 mmφ screen to a 3.0 mmφ screen, and titanium oxide (trade name Typaque A-220: manufactured by Ishihara Sangyo Co., Ltd.) was applied to the pulverized paper. A paper-containing resin composition and an injection molded article for evaluation were the same method except that 1.0% by mass was added and magnesium oxide (trade name: magnesium oxide manufactured by Tomita Pharmaceutical Co., Ltd.) was not added as a neutralizing agent. Got. The paper ratio in this paper-containing resin composition was 55% by mass.

(Comparative Example 1B)
In the manufacture of the pulverized paper of Example 1B, the screen was changed from a 0.5 mmφ screen to a 3.0 mmφ screen, and titanium oxide (trade name Typaque A-220: manufactured by Ishihara Sangyo Co., Ltd.) was applied to the pulverized paper. A paper-containing resin composition and an injection-molded product for evaluation were the same except that an amount of 3.0% by mass was added and magnesium oxide (trade name: Magnesium oxide: manufactured by Tomita Pharmaceutical Co., Ltd.) was not added as a neutralizing agent. Got. The paper ratio in this paper-containing resin composition was 55% by mass.

(Comparative Example 2A)
In the production of the paper-containing resin composition of Example 1A, maleic anhydride (trade name: maleic anhydride: manufactured by Nippon Oil & Fats Co., Ltd.) was changed from 0.5% by mass to additive-free to the pulverized paper, and titanium oxide (product) Name Typaque A-220: manufactured by Ishihara Sangyo Co., Ltd.) was added without addition, and magnesium oxide (trade name: Magnesium oxide: manufactured by Tomita Seiyaku Co., Ltd.) was changed from 0.5% by mass to no addition as a neutralizer. In the same manner, a paper-containing resin composition and an evaluation injection-molded product were obtained.

(Comparative Example 2B)
In the production of the paper-containing resin composition of Example 1B, maleic anhydride (trade name: maleic anhydride: manufactured by Nippon Oil & Fats Co., Ltd.) was changed from 0.5% by mass to no addition with respect to the pulp component, and oxidized as a neutralizing agent. A paper-containing resin composition and an injection molded product for evaluation were obtained in the same manner except that magnesium (trade name: magnesium oxide: manufactured by Tomita Pharmaceutical Co., Ltd.) was changed from 0.5% by mass to no additive with respect to the total mass.

(Comparative Example 3A)
In the production of the paper-containing resin composition of Example 3A, maleic anhydride (trade name: maleic anhydride: manufactured by Nippon Oil & Fats Co., Ltd.) was changed from 0.5% by mass to no additive with respect to the pulverized paper, and titanium oxide (product) A paper-containing resin composition and an evaluation injection-molded product were obtained in the same manner except that the amount of 18.0% by mass was added to the pulverized paper (name Type A-220: manufactured by Ishihara Sangyo Co., Ltd.).

(Comparative Example 3B)
In the production of the paper-containing resin composition of Example 3B, maleic anhydride (trade name: maleic anhydride: manufactured by Nippon Oil & Fats Co., Ltd.) was changed from 1.5% by mass to no addition to the pulp component, and titanium oxide (trade name) (Taipeke A-220: manufactured by Ishihara Sangyo Co., Ltd.) is added in an amount of 18.0% by weight based on the pulverized paper, and magnesium oxide (trade name: Magnesium oxide: manufactured by Tomita Pharmaceutical Co., Ltd.) is used as a neutralizing agent. A paper-containing resin composition and an evaluation injection molded product were obtained in the same manner except that the amount was changed from 1.5% by mass to no addition.

(Comparative Example 4A)
In the production of the paper-containing resin composition of Example 3A, maleic anhydride (trade name: maleic anhydride: manufactured by Nippon Oil & Fats Co., Ltd.) was changed from 1.5% by mass to no additive with respect to the pulverized paper. Name Typaque A-220: manufactured by Ishihara Sangyo Co., Ltd.) was added without addition, and magnesium oxide (trade name: Magnesium oxide: manufactured by Tomita Pharmaceutical Co., Ltd.) was changed from 1.5% by mass to no addition as a neutralizing agent. In the same manner, a paper-containing resin composition and an evaluation injection-molded product were obtained.

  Evaluation of the pulverized paper, the paper-containing resin composition and the evaluation injection-molded product used in the Examples and Comparative Examples was performed by the following methods, and the results are shown in Tables 1 and 2.

<Paper ratio>
The ratio of the paper in the paper-containing resin composition is expressed as a paper ratio, and here, the total amount of paper and fillers such as calcium carbonate is used as the paper material.

<MFR>
ASTM D1238-04c “Standard Test Method for Flow Rates of Thermoplastics by Extrasi
Measured according to “on Plasometer”. Test temperature = 190 ° C., test load = 10 kg. It measured about the paper containing resin composition.

<Fiber dispersibility>
A predetermined amount of carbon black was blended with the paper-containing resin composition to produce an evaluation injection molded product, and the degree of fiber dispersion was evaluated according to the following criteria.
X: Many undispersed fibers, inferior to practical use.
Δ: Some undispersed fibers, slightly inferior and not practical.
○: No undispersed fiber, excellent.

<Moldability>
Workability at the time of molding processing for producing a molded product from the paper-containing resin composition was evaluated according to the following criteria.
X: A molded product was not obtained.
Δ: Formability is poor and cannot be practically used.
○: Good formability.

<Discoloration of injection molded products>
The molded product was judged based on the following criteria based on visual sensation.
X: Clear yellowishness, inferior to practical use.
Δ: Slightly yellowish and inferior to practical use.
○: Excellent without yellow.

<Odor of injection molded products>
The odor of the molded product was determined according to the following criteria.
(Triangle | delta): There is some smell of paper burning, it is inferior and cannot endure practical use.
○: Excellent without odor.

<Tensile strength>
Measured according to JIS K 7113: 1995 “Plastic Tensile Test Method”.

<Bending strength>
Measured according to JIS K 7203: 1995 “Bending test method of hard plastic”.

<IZOD (Izod impact strength)>
Measured according to ASTM D256-04 “Test Methods for Determining of the Pendulum Impact Resistance of Notched Specimens of Plastics” (no notch).

<Water absorption rate>
Measured according to JIS K 7209: 2000 “Plastics—How to Obtain Water Absorption” D method.

  In Examples 1A and 2A, an edge of PPC paper having an LBKP of 95% by mass of fine paper was used, and in Examples 1B and 2B, milk having an NBKP of 90% by mass of the base film of polyethylene film laminated paper was used. A paper-containing resin composition was prepared using carton printed trimming waste. Although both the paper-containing resin compositions of Examples 1A and 2A have a high LBKP content, both of the paper-containing resin compositions of Examples 1B and 2B have a high NBKP content. Nevertheless, since it could be uniformly dispersed by esterification of the pulverized product and kneading by a twin screw extruder, the fiber dispersibility and moldability were good, and the obtained molded product had neither discoloration nor odor. In Examples 1A and 1B, since the addition amount of titanium oxide is large, the heat fluidity (MFR) is improved by the effect.

  In Examples 3A and 4A, a recovered copy paper having a LBKP of 70% by weight of the base paper of the paper is used, and in Examples 3B and 4B, a recovered milk pack having an NBKP of the base paper of the polyethylene film laminated paper of 80% by weight. Was used to prepare a paper-containing resin composition. Although both the paper-containing resin compositions of Examples 3A and 4A have a high LBKP content, the paper-containing resin compositions of Examples 3B and 4B have a high NBKP content. Nevertheless, since it could be uniformly dispersed by esterification of the pulverized product and kneading by a twin screw extruder, the fiber dispersibility and moldability were good, and the obtained molded product had neither discoloration nor odor. In Examples 3A and 3B, since the amount of titanium oxide added is large, the heat fluidity (MFR) is improved by the effect.

  In Example 5A, compared with the formulation of Example 1A, the addition amount of titanium oxide was further increased, and a fluidity improver was added to prepare an injection molded product for evaluation. The fluidity was good as in Example 1A.

  In Comparative Examples 1A and 1B, since the pulverized particle size of the pulverized product is large, the dispersibility becomes insufficient, the fiber part acidity and the moldability are poor, and the neutralizing agent was not added. The product showed discoloration and odor.

  In Comparative Examples 2A to 4A, 2B, and 3B, since maleic anhydride was not added, dispersibility was insufficient and fiber dispersibility and moldability were poor. Moreover, since the neutralizing agent was not added in Comparative Examples 2A, 4A, and 2B, discoloration and odor were observed in the obtained molded product. In Comparative Examples 3A and 3B, the titanium oxide content was high, and the strength was reduced.

The mechanical strength, particularly tensile strength, bending strength, and water absorption were better in the examples than in the comparative examples.

Claims (8)

Pulverized paper esterified with polybasic acid anhydride, a polyolefin resin, a magnesium compound as the alkaline earth metal compound and titanium oxide containing at least, the pulverized material and the polyolefin resin Ri principal component der,
The content of the pulverized product is 50 to 70% by mass,
The content of the polyolefin resin is 15 to 48% by mass,
Content of the said magnesium compound is 0.1-5 mass% with respect to the total mass in conversion of magnesium oxide,
Content of the said titanium oxide is 2-15 mass% with respect to a paper raw material, The paper containing resin composition characterized by the above-mentioned.   The paper-containing resin composition according to claim 1, wherein the polyolefin resin is a polypropylene resin alone or a mixture of a polypropylene resin and a polyethylene resin.   2. The polybasic acid anhydride is maleic anhydride, and the ratio of maleic anhydride introduced by esterification is 0.1 to 5% by mass with respect to the paper material. 2. The paper-containing resin composition according to 2. The paper-containing resin composition according to claim 1, 2 or 3 , wherein the paper is a paper containing 70 mass% or more of exposed kraft pulp. The paper-containing resin composition according to claim 1, 2, 3, or 4 , wherein the content of the pulverized paper material (excluding filler) is 51% by mass or more. Crushing paper containing 70% by weight or more of exposed kraft pulp to obtain a pulverized paper,
Esterifying the pulverized paper with a polybasic acid anhydride;
Kneading a magnesium compound and titanium oxide as ester ground paper, polyolefin resin, alkaline earth metal compound, and neutralizing the organic acid with the alkaline earth metal compound;
A step of further kneading the obtained kneaded product with a twin screw extruder to obtain a paper-containing resin composition;
I have a,
The manufacturing method of the paper containing resin composition characterized by making content of the said titanium oxide into 2-15 mass% with respect to a paper raw material . The method for producing a paper-containing resin composition according to claim 6 , wherein the pulverized particle size of the pulverized paper is 0.5 to 2.5 mm. A paper-containing resin molded article, which is formed of the paper-containing resin composition according to any one of claims 1 to 5 .