Resin material composition and injection molded article

09803076 · 2017-10-31

Assignee

Inventors

Cpc classification

International classification

Abstract

The present invention provides a resin material composition including 25 to 65% by mass of a thermoplastic polyolefin resin, 0.5 to 22% by mass of a glass wool, and 5 to 35% by mass of a thermoplastic elastomer.

Claims

1. A molded article of a resin material composition comprising: a mixture of different thermoplastic polymer materials including a thermoplastic polyolefin resin as a matrix resin and a thermoplastic elastomer; and a glass wool, wherein the thermoplastic polyolefin resin is contained in the resin material composition at a formulation ratio of 25 to 65% by mass, the glass wool is contained in the resin material composition at a formulation ratio of 0.5 to 22% by mass, the glass wool has elongated fibers entangled with each other in an arrangement consistent with cotton and the elongated fibers of the glass wool are bent and contained within the matrix resin, the thermoplastic elastomer is contained in the resin material composition at a formulation ratio of 5 to 35% by mass, and the molded article has a Charpy impact value of 7 KJ/m.sup.2 or more which is measured by carrying out the Charpy impact test ((23° C., notched, a notch: Type A) in accordance with JIS K7111) of the molded resin material.

2. The molded article of a resin material composition according to claim 1, further comprising a non-fibrous inorganic filler in the resin material composition at a formulation ratio of 5 to 35%.

3. The molded article of a resin material composition according to claim 1, wherein the thermoplastic polyolefin resin is contained in the resin material composition at a formulation ratio of 30 to 60% by mass.

4. The molded article of a resin material composition according to claim 2, wherein the thermoplastic polyolefin resin is contained in the resin material composition at a formulation ratio of 30 to 60% by mass.

5. The molded article of a resin material composition according to claim 1, wherein the thermoplastic polyolefin resin in the resin material composition has an MFR (230° C., 2.16 N) of 37 to 120 g/10 min.

6. The molded article of a resin material composition according to claim 2, wherein the thermoplastic polyolefin resin in the resin material composition has an MFR (230° C., 2.16 N) of 37 to 120 g/10 min.

7. The molded article of a resin material composition according to claim 3, wherein the thermoplastic polyolefin resin in the resin material composition has an MFR (230° C., 2.16 N) of 37 to 120 g/10 min.

8. The molded article of a resin material composition according to claim 4, wherein the thermoplastic polyolefin resin in the resin material composition has an MFR (230° C., 2.16 N) of 37 to 120 g/10 min, and a raised height of a weld part of the molded article is 10 μm or less.

9. A resin material composition comprising: a mixture of different thermoplastic polymer materials including a thermoplastic polyolefin resin as a matrix resin and a thermoplastic elastomer; and a glass wool, wherein the thermoplastic polyolefin resin has a hardness greater than a hardness of the thermoplastic elastomer, the thermoplastic polyolefin resin is contained in the resin material composition at a formulation ratio of 25 to 65% by mass, the glass wool is contained in the resin material composition at a formulation ratio of 0.5 to 22% by mass, the glass wool has elongated fibers entangled with each other in an arrangement consistent with cotton and the elongated fibers of the glass wool are bent and contained within the matrix resin, and the thermoplastic elastomer is contained in the resin material composition at a formulation ratio of 5 to 35% by mass.

10. The resin material composition according to claim 9, further comprising a non-fibrous inorganic filler in the resin material composition at a formulation ratio of 5 to 35%.

11. The resin material composition according to claim 9, wherein the thermoplastic polyolefin resin is contained in the resin material composition at a formulation ratio of 30 to 60% by mass.

12. The resin material composition according to claim 10, wherein the thermoplastic polyolefin resin is contained in the resin material composition at a formulation ratio of 30 to 60% by mass.

13. The resin material composition according to claim 9, wherein the thermoplastic polyolefin resin in the resin material composition has an MFR (230° C., 2.16 N) of 37 to 120 g/10 min.

14. The resin material composition according to claim 10, wherein the thermoplastic polyolefin resin in the resin material composition has an MFR (230° C., 2.16 N) of 37 to 120 g/10 min.

15. The resin material composition according to claim 11, wherein the thermoplastic polyolefin resin in the resin material composition has an MFR (230° C., 2.16 N) of 37 to 120 g/10 min.

16. The resin material composition according to claim 12, wherein the thermoplastic polyolefin resin in the resin material composition has an MFR (230° C., 2.16 N) of 37 to 120 g/10 min.

17. An injection molded article comprising the resin material composition as claimed in claim 9 and a raised height of a weld part of the molded article is 10 μm or less.

18. The injection molded article according to claim 17 having a Charpy impact value of 7 KJ/m.sup.2 or more which is measured by carrying out the Charpy impact test ((23° C., notched, a notch: Type A) in accordance with JIS K7111) of the molded resin material.

19. The molded article of a resin material composition according to claim 1, wherein the glass wool has an average fiber diameter of 3 to 20 μm and an average aspect ratio of 10 to 100.

20. The resin material composition according to claim 9, wherein the glass wool has an average fiber diameter of 3 to 20 μm and an average aspect ratio of 10 to 100.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1A is a perspective view illustrating an injection molded article used for a measurement test of the raised height of a weld part, FIG. 1B is a plane view illustrating a test specimen cut off from the injection molded article, and FIG. 1C is a graph illustrating the surface height of the test specimen.

DESCRIPTION OF EMBODIMENTS

(2) [1] The thermoplastic polyolefin resin is not particularly limited, but examples thereof include polyethylene, polypropylene, polybutadiene, and polycycloolefin. Among them, polypropylene or polyethylene is preferable. This is because both mechanical performance and low cost are required for injection molded articles for automobiles and the like and these resins satisfy both requirements. Here, when a component is simply called a resin in this specification, an elastomer is not included.

(3) MFR (230° C., 2.16 N) of the thermoplastic polyolefin resin is not particularly limited, and the MFR is preferably 37 to 120 g/10 min. The resin having an MFR of 37 g/10 min or more allows glass wool to be easily and uniformly diffused to a terminal weld part and thus appearance smoothness can be easily obtained. On the other hand, few appropriate resins having an MFR of more than 120 g/10 min exist and thus the implementation of the present invention is difficult. Therefore, the MFR is preferably 120 g/10 min or less.

(4) [2] The material of the glass wool is not particularly limited, but examples thereof include quartz glass, and tempered glass.

(5) The average fiber diameter of the glass wool is not particularly limited and is preferably 3 to 20 μm due to the following reason. The glass wool having an average fiber diameter of 3 μm or more is expected to have a reinforcement effect (improved impact resistance). On the other hand, the glass wool having an average fiber diameter of more than 20 μm may exist independently in a linear state in the matrix resin (thermoplastic polyolefin resin) due to difficulty in entanglement of the fibers of the glass wool with each other. Consequently, a high aspect ratio in addition to the above described state may decrease flowability due to the glass wool fibers linearly extending in a hard and long state. This may lead to poor surface appearance. In addition, the glass wool in a linear state may be oriented in a resin flow direction (MD) at the weld part and warpage may also occur due to what is called a spring-back phenomenon, causing adverse effects on the appearance of the weld part and rigidity. In that respect, the glass wool having an average fiber diameter of 20 μm or less is difficult to be in a linear state (difficult to orient) due to flexibility and easy deformation of the glass wool at the time of injection molding, and thus it is expected that the glass wool does not have a significant adverse effect on the appearance (flowability) and the rigidity even if the aspect ratio is high.

(6) The average aspect ratio of the glass wool is not particularly limited and the average aspect ratio is preferably 10 to 100 due to the following reason. The glass wool having an average fiber diameter in the above-described range and an average aspect ratio of 10 or more may result in easy entanglement of the fibers of the glass wool with each other and thus the glass wool may exist in a cotton-like state in which the elongated fibers of the glass wool are bent in the matrix resin. Consequently, the glass wool is expected to be substantially uniformly filled to the terminal thin-walled part (weld part) without being separated from the resin at the time of injection molding. In addition, warpage and a sink mark like shrinkage unevenness along the resin flow direction (MD) and the vertical direction (TD) of MD can be expected to be reduced because the glass wool does not exist in a linear state (exists in a cotton-like state). On the other hand, a glass wool having a too excessively high aspect ratio is difficult to be produced and thus the average aspect ratio is preferably 100 or less as described above.

(7) The surface of the glass wool may not be treated or may be treated with various surface treatment agents. The surface treatment agent of the glass wool is not particularly limited, but examples thereof include a silane coupling agent, a fatty acid, a fatty acid ester, and a carboxylic acid.

(8) [3] The non-fibrous inorganic filler is not particularly limited, but examples thereof include talc, calcium carbonate, kaolin clay, and mica.

(9) The surface of the non-fibrous inorganic filler may not be treated or may be treated with various surface treatment agents The surface treatment agent of the non-fibrous inorganic filler is not particularly limited, but examples thereof include a silane coupling agent, a fatty acid, a fatty acid ester, and a carboxylic acid,

(10) [4] The thermoplastic elastomer is not particularly limited, but examples thereof include various elastomers such as polyolefin elastomers, polystyrene elastomers, polyester elastomers, polyurethane elastomers, polyamide elastomers, acrylic elastomers, vinyl chloride elastomers, and fluorine elastomers.

(11) [5] A method for producing the resin material composition of the present invention is not particularly limited, but examples thereof include a form of melting and kneading the components with an extruder, a mixer, rolls, or the like to obtain the resin material composition.

(12) [6] The present invention is suitable for applications such as outer panels and interior and exterior parts of automobiles. Other than the application to automobiles, the present invention can be applied to various applications. For example, the present invention can be also applied to outer panels and interior and exterior parts of railway cars and various architectural structures, and housings and parts of electric appliances

EXAMPLE

(13) The resin material compositions of Examples 1 to 10 and Comparative Examples 1 to 3 shown in Table 1 were formulated and prepared. An injection molded article was formed from each of the resin material compositions by injection molding, and the physical properties of the articles were tested.

(14) TABLE-US-00001 TABLE 1 Example 1 Example 2 Example 3 Example 4 Matrix Resin Polypropylene 50 Resin (I) Polypropylene 50 Resin (II) Polypropylene 50 Resin (III) Polypropylene Resin (IV) Polyethylene 60 Resin Fibrous Glass Wool 8 10 2 20 Glass Filler Glass Fiber Talc (I) 2 22 30 5 15 Inorganic Talc (II) 20 Finer Calcium 10 10 Carbonate Thermoplastic Elastomer (I) 20 10 Elastomer Elastomer (II) 20 Elastomer (III) 20 TOTAL 100 90 102 105 Formulation MatrixResin (%) 50 55.56 49.02 57.14 Ratio Glass Wool (%) 8 11.11 1.96 19.05 Glass Fiber (%) Inorganic 22 11.11 29.41 14.29 Filler (%) Elastomer (%) 20 22.22 19.61 9.52 Tensile Modulus (GPa) 3.3 2.2 2.7 2.5 Charpy Impact Value (kJ/m.sup.2) 15 12 18 12 Appearance Raised Height 5 7 10 7 of Weld Part (μm) Visual Good Good Good Good Observation of Weld Example 5 Example 6 Example 7 Example 8 Matrix Polypropylene 55 40 60 Resin Resin (I) Polypropylene 40 Resin (II) Polypropylene 20 Resin (III) Polypropylene Resin (IV) Polyethylene 40 Resin Fibrous Glass Wool 5 1 10 5 Glass Filler Glass Fiber Inorganic Talc (I) 15 30 5 20 7 27 Filler Talc (II) 10 15 5 10 Calcium 10 10 Carbonate Thermoplastic Elastomer (I) 30 25 30 Elastomer Elastomer (II) 30 10 Elastomer (III) 20 5 8 TOTAL 100 101 100 100 Formulation Matrix Resin (%) 55 39.60 40 6 Ratio Glass Wool (%) 5 0.99 10 5 Glass Fiber (%) Inorganic 10 29.70 20 27 Filler (%) Elastomer (%) 30 29.70 30 8 Tensile Modulus (GPa) 2.0 2.1 2.3 2.8 Charpy Impact Value (kJ/m.sup.2) 25 30 15 12 Appearance Raised Height 5 7 10 5 of Weld Part (μm) Visual Good Good Good Good Observation of Weld Comparative Comparative Comparative Example 9 Example 10 Example 1 Example 2 Example 3 Matrix Resin Po1ypropylene Resin (I) Polypropylene 30 60 52 Resin (II) Polypropylene 55 Resin (III) Polypropylene 40 Resin (IV) Polyethylene Resin Fibrous Glass Wool 22 10 22 25 Glass Filler Glass Fiber 8 Inorganic Talc (I) 8 15 15 25 8 Filler Talc (II) 10 10 Calcium 30 5 Carbonate Thermoplastic Elastomer (I) 10 15 27 10 15 Elastomer Elastomer (II) 5 3 5 Elastomer (III) 30 TOTAL 100 100 100 100 100 Formulation MatrixResin (%) 55 30 60 40 52 Ratio Glass Wool (%) 22 10 22 25 Glass Fiber (%) 8 Inorganic 8 30 15 25 8 Filler (%) Elastomer (%) 15 30 3 27 15 Tensile Modulus (GPa) 3.1 3.3 3.2 2.2 3.4 Charpy Impact Value (kJ/m.sup.2) 12 7 2 10 10 Appearance Raised Height 9 5 15 25 12 of Weld Part (μm) Visual Good Good Poor Poor Poor Observation of Weld

(15) In Table 1, the values in each column of “Matrix resin”, “Fibrous glass filler”, “Inorganic filler”, and “Thermoplastic elastomer” are relative mass (in columns having a right column and left columns, a plurality of materials are used together and values in the left columns indicate a mass of each of the materials and the value in the right column indicates the subtotal of the masses in the left columns) and the total of the relative masses is not always 100 Thus, the values determined by converting the relative value into % by mass are listed in “Formulation ratio”. Specific materials used, test methods of physical properties, and the like are as follows.

(16) [Matrix Resins]

(17) Polypropylene Resin (I) is “BX3920” (trade name, manufactured by SI<Global Chemical Co., Ltd., specific gravity 0.93, flexural modulus 1.9 GPa, Izod impact strength (23° C., notched) 6 kJ/m.sup.2, melt viscosity (MFR) (230° C., 2.16 N) 100 g/10 min, heat deflection temperature under load (HDT) (0.45 MPa) 135° C., Rockwell hardness 105, tensile strength (TS) 33 MPa, and elongation at break (EB) less than 100%.

(18) Polypropylene Resin (II) is “BH975MO” (trade name, manufactured by Borouge PTE LTD., specific gravity 0.91, flexural modulus 1.5 GPa, izod impact strength (23° C., notched) 8 kJ/m.sup.2, melt viscosity (MFR) (230° C., 2.16 N) 38 g/10 min, heat deflection temperature under load (HDT) (0.45 MPa) 96° C., Rockwell hardness 86, tensile strength (TS) 25 MPa, and elongation at break (EB) 4%).

(19) Polypropylene Resin (III) is “NOVATEC PP BC10BH ” (trade name, manufactured by Japan Polypropylene Corporation, specific gravity 0.90, flexural modulus 1.6 GPa, Izod impact strength (23° C., notched) 3.5 kJ/m.sup.2, melt viscosity (MFR) (230° C., 2.16 N) 119 g/10 min, heat deflection temperature under load (HDT) (0.45 MPa) 108° C., Rockwell hardness 105, tensile strength (TS) 32.5 MPa, and elongation at break (EB) 6%).

(20) Polypropylene Resin (IV) and the glass fibers are a polypropylene resin and glass fibers contained in the glass fiber reinforced resin “PP-GF-50-02” (trade name, manufactured by Daicel. Polymer Ltd.). In other words, this glass fiber reinforced resin is formed by adding the glass fibers to Polypropylene Resin (IV). The inorganic fillers and the thermoplastic elastomer are further added to the glass fiber reinforced resin to be adjusted to the formulation of Comparative Example 2 in Table 1.

(21) Polyethylene Resin is “H6007JU” (trade name, manufactured by SCG Chemicals Co., Ltd., specific gravity 0.96, flexural modulus 1.4 GPa, izod impact strength (23° C., notched) 3.5 kJ/m.sup.2, melt viscosity (MFR) (190° C., 2.16 N) 7.5 g/10 min, heat deflection temperature under load (HDT) (0.45 MPa) 75° C., hardness (Shore D) 68, tensile strength (TS) 31 MPa, and elongation at break (BB) greater than 650%).

(22) [Fibrous Glass Fillers]

(23) Glass wools are trial products manufactured by NANODAX CO., Ltd. (no trade name) (average fiber diameter 4 μm and average aspect ratio 100).

(24) [Inorganic Fillers]

(25) Talc (I) is “GH7” (trade name, manufactured by HAYASHI KASEI CO., LTD.). Talc (II) is “NTT05” (trade name, manufactured by IMI FABI Talc Company) Calcium carbonate is “Vigot-15” (trade name, manufactured by Shiraishi Kogyo Co., Ltd.).

(26) [Thermoplastic Elastomers]

(27) Elastomer (I) is “TAFMER DF610” (trade name, manufactured by Mitsui Chemicals, Inc. specific gravity 0.86, melt viscosity (MFR) (230° C., 2.16 N) 2.2 g/10 min, melt viscosity (MFR) (190° C., 2.16 N) 1.2 g/10 min, hardness (Shore A) 57, tensile strength (TS) greater than 3 MPa, and elongation at break (ED) greater than 1,000%).

(28) Elastomer (II) is “ENGAGE 8842 ”(trade name, manufactured by Dow Chemical. Company, specific gravity 0.86, melt viscosity (MFR) (190° C., 2.16N) 1.0 g/10 min, hardness (Shore A) 54, tensile strength (TS) 3 MPa, and elongation at break (ED) 1,200%)

(29) Elastomer (III) is “SEPTON 2063” (trade name, manufactured by KURARAY CO., LTD., specific gravity 0.88, melt viscosity (MFR) (230° C., 2.16 N) 7.0 g/10 min, hardness (Shore A) 36, tensile strength (TS) 10.8 MPa, and elongation at break (EB) 1200%).

(30) [Test Methods for Physical Properties]

(31) Tensile modulus was measured by carrying out the tensile test in accordance with JIB K7161 The shape of the test specimen was determined to be Type 1A, the tensile speed was determined to be 1 mm/min, and the gauge length was determined to be 50 mm. Charpy impact value was measured by carrying out the Charpy impact test (23° C., notched) in accordance with JIS K7111. The notch was Type A.

(32) The raised height of a weld part was measured as follows The resin material composition was injected into a mold through two gates (distance between centers of the gates 300 mm) (resin temperature 175 to 200° C., mold temperature 80° C., and holding pressure 20 MPa) to carry out the injection molding of the plate-like injection molded article having a length of 600 mm, a width of 146 mm, and a thickness of 2 mm. Subsequently, a test specimen including the weld part was cut off from the center part of the plate-like injection molded article as illustrated in FIG. 1A. Specifically, the test specimen was a test specimen having a length of 30 mm and a width of 10 mm, and, as illustrated in FIG. 1B, was cut off so that the weld part extending to the width direction was located at the center of the test specimen in the length direction. Subsequently, the height of the weld part and the height of the surface around the weld part of the test specimen were measured in a range of about 20 mm in the length direction of the test specimen with a laser microscope. By this measurement, for example, the graph illustrated in FIG. 1C is obtained. The height difference between the base line and the weld peak in this graph is determined to be the raised height of the weld part. The laser microscope described above is “VK-X100” (trade name, manufactured by KEYENCE CORPORATION),

(33) “Visual observation of weld” shows whether appearance at and around the weld part is good or poor when visually determined. “Good” shows that the appearance was determined to be good, and “Poor” shows that the appearance was determined to be poor.

(34) [Physical Properties]

(35) As shown in Table 1, any of tensile modulus, Charpy impact value, and raised height of the weld part (visual observation) are not good in the injection molded articles of Comparative Examples 1 to 3, whereas the injection molded articles of Examples 1 to 10 have a tensile modulus of 2.0 to 3.3 GPa, a Charpy impact value of 7 to 30 KJ/m.sup.2, and a raised height of the weld part of 5 to 10 μm, (visually good), which are good and well-balanced.

(36) The present invention is not limited to Examples and can be changed and embodied appropriately without departing from the scope and spirit of the invention.