JP2020164804A - Resin composition - Google Patents

Abstract

To provide a resin composition excellent in surface wettability without depending on post-treatment.SOLUTION: The resin composition includes a polyolefin based resin and a polyvinyl acetal resin (except a polyvinyl formal resin). The melt flow rate of a resin base material including the polyolefin based resin except the polyvinyl acetal resin is in a range of 0.01 g/10 minutes or more and 4 g/10 minutes or less, and the weight ratio of the content of the polyolefin based resin to the content of the polyvinyl acetal resin is in a range of the polyolefin based resin:the polyvinyl acetal resin=99.9:0.1-0.1:99.9.SELECTED DRAWING: Figure 1

Description

The present invention relates to a resin composition, and more particularly to a resin composition having hydrophilicity.

Plastics such as polypropylene (PP) generally have low surface wettability, and it is difficult to print or paint on a molded product. As a method for improving the wettability of plastic, there are methods such as corona discharge, frame treatment, chemical treatment, and primer treatment. The method using corona discharge or frame processing has problems that the device is expensive, the wettability does not last long, and it is not suitable for a complicated shape. In chemical treatment, it is necessary to use a chemical solution containing harmful substances such as chromium. In the primer treatment, it was necessary to dry the solvent, and the heat resistance was low. Therefore, an attempt has been made to mold a plastic in which the hydrophilic components are dispersed by mixing and kneading the hydrophilic components at the time of molding the plastic (see, for example, Patent Document 1). However, even with this method, there is a problem that the hydrophilic component does not appear on the surface of the molded product and the desired hydrophilicity cannot be obtained, or the hydrophilic component becomes a defect and becomes brittle. Further, in the technique of Patent Document 1, it is essential to add an interphase mediator in order to enhance the affinity of each component, and the cost merit is small.

Japanese Unexamined Patent Publication No. 7-149996

The present invention solves the above problems, and aims to obtain a resin composition having good surface wettability without any post-treatment, focusing on the viscosity of the constituent components.

In order to achieve the above object, the resin composition of the present invention contains a polyolefin-based resin and a polyvinyl acetal resin (excluding polyvinyl formal resin).
The melt flow rate of the resin base material containing the polyolefin-based resin excluding the polyvinyl acetal resin is within the range of 0.01 g / 10 minutes or more and 4 g / 10 minutes or less.
The weight ratio of the content of the polyolefin resin to the content of the polyvinyl acetal resin is within the range of polyolefin resin: polyvinyl acetal resin = 99.9: 0.1: 0.1: 99.9. It is characterized by.

In the resin composition of the present invention, it is preferable that the resin base material further contains a rubber composition, and the rubber composition includes ethylene propylene rubber, ethylene propylene diene rubber, butadiene rubber, styrene butadiene rubber, nitrile rubber, and isoprene rubber. , And at least one selected from the group consisting of mixtures thereof.

In the resin composition of the present invention, the polyvinyl acetal resin is preferably at least one selected from the group consisting of polyvinyl acetal acetal and polyvinyl butyral.

In the resin composition of the present invention, the polyolefin-based resin is preferably at least one selected from the group consisting of polypropylene resin and polyethylene resin.

The resin composition of the present invention preferably further contains a radical generator.

According to the present invention, paying attention to the viscosity of the constituent components, it is possible to obtain a resin composition having good surface wettability without post-treatment.

1 (A) to 1 (D) are infrared spectroscopic spectra of the resin composition of the present invention and the resin composition of Comparative Example. The resin composition has a weight ratio of polypropylene: polyvinyl butyral = 75:25. 2 (A) to 2 (D) are infrared spectroscopic spectra of the resin composition of the present invention and the resin composition of Comparative Example. The weight ratio of the resin composition is polypropylene: polyvinyl butyral: ethylene propylene diene rubber = 50:25:25. 3 (A) and 3 (B) are infrared spectroscopic spectra of the resin composition of the comparative example, comparing the presence or absence of the rubber composition with the same resin. 4 (A) and 4 (B) are infrared spectroscopic spectra of the resin composition of the present invention. The weight ratio of the resin composition is polypropylene: polyvinyl butyral: ethylene propylene diene rubber = 50:25:25. 5 (A) and 5 (B) are infrared spectroscopic spectra of the resin composition of the present invention. The resin composition has a weight ratio of high density polyethylene: polyvinyl butyral = 75:25. 6 (A) and 6 (B) are infrared spectroscopic spectra of the resin composition of the present invention. The resin composition has a weight ratio of high density polyethylene: polyvinyl butyral: ethylene propylene diene rubber = 50:25:25. 7 (A) and 7 (B) are infrared spectroscopic spectra of the resin composition of the comparative example. The resin composition has a low weight ratio of polyethylene: polyvinyl butyral = 75:25. 8 (A) and 8 (B) are infrared spectroscopic spectra of the resin composition of the present invention. The resin composition has a low density polyethylene: polyvinyl butyral: ethylene propylene diene rubber = 50:25:25 by weight ratio. 9 (A) and 9 (B) are infrared spectroscopic spectra of the resin composition of the present invention. The resin composition has a weight ratio of linear low-density polyethylene: polyvinyl butyral = 75:25. 10 (A) and 10 (B) are infrared spectroscopic spectra of the resin composition of Example 8 and the resin composition of Comparative Example 4. The resin composition has a weight ratio of polypropylene: polyvinyl butyral containing a plasticizer = 75:25. FIG. 11 is a diagram showing the results of measuring the impact resistance of the base material and the test pieces obtained in Examples 11 to 13 in the temperature range from room temperature (23 ° C.) to −40 ° C.

Hereinafter, preferred embodiments of the present invention will be described in detail. The resin composition of the present invention contains a polyolefin resin and a polyvinyl acetal resin (excluding polyvinyl formal resin), and the melt flow rate of the resin base material containing the polyolefin resin excluding the polyvinyl acetal resin is 0. It is in the range of .01 g / 10 minutes or more and 4 g / 10 minutes or less, and the weight ratio of the content of the polyolefin resin to the content of the polyvinyl acetal resin is determined as polyolefin resin: polyvinyl acetal resin = 99.9: By setting the content in the range of 0.1 to 0.1: 99.9, it was possible to realize a resin composition having good surface wettability without post-treatment. The melt flow rate (MFR) of the polyolefin-based resin is a value indicating a physical property value related to the viscosity of the resin, and is measured by a standard test method of JIS K7210-1. In the present invention, MFR is a value measured under measurement conditions of 2.16 kg and 230 ° C. (conditions specified for polypropylene resin in JIS K6921-2).

In the resin composition of the present invention, the melt flow rate of the resin base material containing the polyolefin resin excluding the polyvinyl acetal resin shall be within the range of 0.01 g / 10 minutes or more and 4 g / 10 minutes or less. It was found that even if the polyvinyl acetal resin having a molecular weight exceeding 100,000 is added, more OH groups (hydrophilic components) can be exposed on the surface as compared with the cross section.

The polyvinyl acetal resin is preferably at least one selected from the group consisting of polyvinyl acetal acetal and polyvinyl butyral. The molecular weight of the polyvinyl acetal resin is preferably 1,000 or more, more preferably 10,000 or more. According to the present invention, the molecular weight of the polyvinyl acetal resin may be in the range of 1.0 × 10 ⁵ or more. Further, the weight ratio of the content of the polyolefin resin to the content of the polyvinyl acetal resin is preferably in the range of polyolefin resin: polyvinyl acetal resin = 99.5: 0.5 to 50:50. , More preferably in the range of 99: 1 to 75:25.

The polyolefin resin is preferably at least one selected from the group consisting of polypropylene resins, polyethylene resins, and various copolymers containing the resins as main components. It is particularly preferable that the polyolefin resin is at least one selected from the group consisting of polypropylene resin and polyethylene resin. Further, as the polyolefin resin, one type may be blended alone, or two or more types of polyolefin resins may be used in combination.

It is preferable that the resin composition further contains a rubber composition. The rubber composition is a group consisting of ethylene propylene rubber (EPM), ethylene propylene diene rubber (EPDM), butadiene rubber (BR), styrene butadiene rubber (SBR), nitrile rubber (NR), isoprene rubber, and a mixture thereof. It is preferable that it is at least one selected from the above. As the rubber composition, one type may be blended alone, or two or more types of the rubber composition may be used in combination.

In addition, when the resin composition of the present invention further contains a rubber composition, it is possible to further improve the impact resistance while providing the wettability of the surface, and it can be applied to more applications. Therefore, it is preferable.

The resin composition of the present invention further comprises, as any other components, general additives such as inorganic fillers, organic fillers, pigments, dyes, radical initiators, plasticizers, flame retardants and antioxidants. It may be included within a range that does not impair the effect of.

The radical initiator is used to promote the hydrogen abstraction reaction (activation of the constituent components) and the cross-linking reaction between the activated components. Examples of the radical initiator include an organic radical initiator or an inorganic radical initiator, and an organic radical initiator is generally used. Examples of the organic radical initiator include azo compounds and organic peroxides, but organic peroxides are preferable. Further, examples of the organic peroxide include dicumyl peroxide, di-t-butyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butyl peroxy) hexane, and the like. 2,5-dimethyl-2,5-di (t-butylperoxide) hexin-3, t-butylcumyl peroxide, 1,3-bis (t-butylperoxyisopropyl) benzene, 3,6,9-triethyl- 3,6,9-trimethyl-1,4,7-tripeloxonan, 1,1-di (t-hexylperoxy) cyclohexane, 1,1-di (t-hexylperoxy) -3,3,5-trimethyl Cyclohexane, 1,1-di (t-butylperoxy) cyclohexane, 2,2-di (t-butylperoxy) butane, 1,1-di (t-butylperoxy) -2-methylcyclohexane, 2,5-dimethyl -2,5-di (t-hexyl peroxy) hexane, di (2-t-butyl peroxyisopropylhexyl) benzene, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di (2-ethylhexa) Noyl Peroxy) Hexanoate, 1,1,3,3-Tetramethylbutylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t -Butylperoxylaurate, t-butylperoxy-3,3,5-trimethylhexanoate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxyisopropylmonocarbonate, t-hexylperoxy-2-ethylhexylmonocarbonate, 2 , 5-Dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, t-hexylperoxybenzoate, t-butylperoxybenzoate and the like. Among these, it is preferable to use dicumyl peroxide or 2,5-dimethyl-2,5-di (t-butylperoxy) hexane suitable for use at a high temperature such as in an extruder. The radical initiator may be used alone or in combination of two or more.

The blending amount of the radical initiator (crosslinking agent) is preferably 0.01 to 5 parts by weight, more preferably 0.5 to 3 parts by weight, based on 100 parts by weight of the polyvinyl acetal resin. It is more preferably 0 to 2.0 parts by weight.

When the radical initiator is blended in the resin composition, hydrogen is extracted from the constituent components such as the polyvinyl acetal resin to cause a radical reaction, and the constituent components can be chemically bonded to each other. Therefore, the present resin composition is less likely to peel off at the component interface and is less likely to break even when subjected to an impact. That is, according to the resin composition of the present embodiment, excellent toughness can be obtained.

Further, as the plasticizer, it is preferable to use an ester compound having an ether bond in the molecule because it has a good affinity with a polyvinyl acetal resin such as PVB. Specific examples thereof include diethylene glycol di-2-ethylhexanoate, triethylene glycol di-n-hexanoate, diethylene glycol di-n-hexanoate, and triethylene glycol di-2-ethylhexanoate. Particularly preferable esters include triethylene glycol di-2-ethylhexanoate and the like.

The resin composition of the present invention can be produced, for example, by putting each material into a kneader, kneading them, and then producing them with an extrusion molding machine. If necessary, the obtained resin composition may be pelletized or processed into a sheet.

In the resin composition of the present invention, the resin composition further containing the rubber composition has excellent impact resistance, and is therefore preferably used as a material for pallets and containers, and synthetic wood, for example.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

[Example 1, Comparative Example 1]
The results of using polypropylene having different melt flow rates as the polyolefin resin and adding two kinds of polyvinyl acetal resins having different molecular weights separately are shown.

FIG. 1 shows high molecular weight polypropylene (PP, “Novatec” EA9, manufactured by Nippon Polypro Co., Ltd., MFR = 0.52) and polypropylene (PP, homopolymer “Nobrene” Y501N, Sumitomo Chemical Industries, Ltd.) as polyolefin resins. Infrared spectroscopic spectrum of a test piece obtained by kneading with polypropylene butyral (PVB) as a polyvinyl acetal resin at a weight ratio of PP: PVB = 75: 25 and injection molding using MFR = 13.1). Is. 1 (A) is, MFR polypropylene and the molecular weight of 0.52 g / 10 min was used 1.9 × 10 ⁴ of PVB ( "S-LEC B · K" BL-1, manufactured by Sekisui Chemical Co., Ltd.) Test use pieces, FIG. 1 (B), MFR is 0.52 g / 10 min polypropylene and molecular weight of 1.1 × 10 ⁵ of PVB ( "S-LEC B · K" BH-3, manufactured by Sekisui Chemical Co., Ltd.) It is an infrared spectroscopic spectrum of the test piece. Figure 1 (C) is, MFR polypropylene and the molecular weight of 13.1 g / 10 min was used 1.9 × 10 ⁴ of PVB ( "S-LEC B · K" BL-1, manufactured by Sekisui Chemical Co., Ltd.) Test use pieces, FIG. 1 (D) is, MFR is 13.1 g / 10 min polypropylene and molecular weight of 1.1 × 10 ⁵ of PVB ( "S-LEC B · K" BH-3, manufactured by Sekisui Chemical Co., Ltd.) It is an infrared spectroscopic spectrum of the test piece. In the figure, the solid line shows the infrared spectroscopic spectrum on the surface of the test piece, and the broken line shows the infrared spectroscopic spectrum on the cross section of the test piece.

In a polypropylene (EA9) system with an MFR of 0.52 g / 10 min, OH is used on the surface regardless of whether a high molecular weight acetal resin (BH-3) or a low molecular weight acetal resin (BL-1) is used. It can be seen that the peak (around 3300 cm ^-1 ) of the portion identified based on the group appears (Example 1).

On the other hand, in a polypropylene (Y501N) system having an MFR of 13.1 g / 10 min, when a low molecular weight acetal resin (BL-1) is used, the peak (3300 cm ^{-1) of the} portion identified as an OH group on the surface is used. It can be seen that (nearby) appears. On the other hand, when the high molecular weight acetal resin (BH-3) is used, the peak (around 3300 cm ^-1 ) of the portion identified as the OH group does not appear on the surface and exists only in the cross section. (Comparative Example 1).

As described above, by using a polyolefin resin having a melt flow rate of 4 g / 10 minutes or less, even if the polyvinyl acetal resin having a molecular weight exceeding 100,000 is added, the surface is larger than the cross section. It was found that it is possible to obtain a resin composition having good surface wettability by exposing the OH group (hydrophilic component) of the above.

[Example 2, Comparative Example 2]
The results of using polypropylene having different melt flow rates as the polyolefin-based resin, further containing a rubber composition in the resin base material, and separately adding two types of polyvinyl acetal resins having different molecular weights are shown.

FIG. 2 shows high molecular weight polypropylene (PP, “Novatec” EA9, manufactured by Nippon Polypro Co., Ltd., MFR = 0.52) and polypropylene (PP, homopolymer “Noblene” Y501N, Sumitomo Chemical Industries, Ltd.) as polyolefin resins. , MFR = 13.1), polyvinyl butyral (PVB) as the polyvinyl acetal resin, and ethylene propylene diene rubber (EPDM, "ESPRENE505", manufactured by Sumitomo Chemical Industries, Ltd.) as the rubber composition. It is an infrared spectroscopic spectrum of a test piece obtained by kneading with PP: PVB: EPDM = 50: 25: 25 and injection molding. In the above, the MFR of the resin base material (PP + EPDM) was 1.7 g / 10 minutes in the case of EA9 and 4.5 g / 10 minutes in the case of Y501N.

2 (A) is, use an MFR of 1.7 g / 10 min the resin matrix and molecular weight of 1.9 × 10 ⁴ of PVB ( "S-LEC B · K" BL-1, manufactured by Sekisui Chemical Co., Ltd.) There specimen, FIG. 2 (B), MFR is 1.7 g / 10 min the resin matrix and molecular weight of 1.1 × 10 ⁵ of PVB ( "S-LEC B · K" BH-3, manufactured by Sekisui Chemical Co., Ltd. It is an infrared spectroscopic spectrum of a test piece using (manufactured by). FIG. 2 (C), use an MFR of 4.5 g / 10 min the resin matrix and molecular weight of 1.9 × 10 ⁴ of PVB ( "S-LEC B · K" BL-1, manufactured by Sekisui Chemical Co., Ltd.) There specimen, FIG. 2 (D) are, MFR is 4.5 g / 10 min the resin matrix and molecular weight of 1.1 × 10 ⁵ of PVB ( "S-LEC B · K" BH-3, manufactured by Sekisui Chemical Co., Ltd. It is an infrared spectroscopic spectrum of a test piece using (manufactured by). In the figure, the solid line shows the infrared spectroscopic spectrum on the surface of the test piece, and the broken line shows the infrared spectroscopic spectrum on the cross section of the test piece.

In the system of the resin base material (EA9) having an MFR of 1.7 g / 10 minutes, the cross section is cross-sectional regardless of whether the high molecular weight acetal resin (BH-3) or the low molecular weight acetal resin (BL-1) is used. It can be seen that more peaks (around 3300 cm ^-1 ) of the portion identified as the OH group appear on the surface as compared with (Example 2).

On the other hand, in the system of the resin base material (Y501N) having an MFR of 4.5 g / 10 minutes, both the low molecular weight acetal resin (BL-1) and the high molecular weight acetal resin (BH-3) were identified as OH groups. The peak (around 3300 cm ^-1 ) of the portion to be formed is expressed on the surface to the same extent (Comparative Example 2). FIG. 3 is a comparison of the presence or absence of the rubber composition in the same resin, FIG. 3 (A) is a reprint of FIG. 1 (D), and FIG. 3 (B) is a reprint of FIG. 2 (D). .. When a high molecular weight acetal resin (BH-3) is used and a resin base material containing no rubber composition is used (FIG. 3 (A), Comparative Example 1, MFR = 13.1), rubber When the resin base material containing the composition was used (FIG. 3 (B)), uneven distribution of only the cross section was not observed, but it could not be said that it was clearly expressed on the surface.

As described above, by using a polyolefin resin having a melt flow rate of 4 g / 10 minutes or less and further containing a rubber composition in the resin base material, the polyvinyl acetal resin having a molecular weight exceeding 100,000 is added. However, it was found that it is possible to expose more OH groups (hydrophilic components) to the surface as compared with the cross section to obtain a resin composition having good surface wettability.

[Example 3]
"Nobrene" AY564 (polypropylene (PP), manufactured by Sumitomo Chemical Industries, Ltd., MFR = 14.9) is used as the polyolefin resin, polyvinyl butyral (PVB) is used as the polyvinyl acetal resin, and ethylene propylene diene is used as the rubber composition. The infrared spectroscopic spectrum of a test piece obtained by kneading rubber (EPDM, "ESPRENE505", manufactured by Sumitomo Chemical Industries, Ltd.) at a weight ratio of PP: PVB: EPDM = 50: 25: 25 and injection molding is shown. Shown in 4. In the above, the MFR of the resin base material (PP + EPDM) was 3.9 g / 10 minutes.

FIG. 4 (A) shows a test piece using PVB having a molecular weight of 1.9 × 10 ⁴ (“ESREC BK” BL-1, manufactured by Sekisui Chemical Co., Ltd.), and FIG. 4 (B) shows a molecular weight. 1.1 × 10 ⁵ of PVB ( "S-LEC B · K" BH-3, manufactured by Sekisui Chemical Co., Ltd.) is an infrared spectrum of the test piece was used. In the figure, the solid line shows the infrared spectroscopic spectrum on the surface of the test piece, and the broken line shows the infrared spectroscopic spectrum on the cross section of the test piece.

In the resin base material system with an MFR of 3.9 g / 10 minutes, the cross section was compared regardless of whether the high molecular weight acetal resin (BH-3) or the low molecular weight acetal resin (BL-1) was used. It can be seen that more peaks (around 3300 cm ^-1 ) of the portion identified as the OH group appear on the surface.

[Example 4]
High-density polyethylene (HDPE, "Novatec HD" HF313, manufactured by Nippon Polyethylene Co., Ltd., MFR = 0.065) is used as the polyolefin resin, polyvinyl butyral (PVB) is used as the polyvinyl acetal resin, and HDPE: PVB = by weight. The infrared spectroscopic spectrum of the test piece obtained by kneading at 75:25 and injection molding is shown in FIG.

FIG. 5 (A) shows a test piece using PVB having a molecular weight of 1.9 × 10 ⁴ (“ESREC BK” BL-1, manufactured by Sekisui Chemical Co., Ltd.), and FIG. 5 (B) shows a molecular weight. 1.1 × 10 ⁵ of PVB ( "S-LEC B · K" BH-3, manufactured by Sekisui Chemical Co., Ltd.) is an infrared spectrum of the test piece was used. In the figure, the solid line shows the infrared spectroscopic spectrum on the surface of the test piece, and the broken line shows the infrared spectroscopic spectrum on the cross section of the test piece.

In the resin base material system with an MFR of 0.065 g / 10 minutes, the cross section was compared regardless of whether the high molecular weight acetal resin (BH-3) or the low molecular weight acetal resin (BL-1) was used. It can be seen that more peaks (around 3300 cm ^-1 ) of the portion identified as the OH group appear on the surface.

[Example 5]
High-density polyethylene (HDPE, "Novatec HD" HF313, manufactured by Nippon Polyethylene Co., Ltd., MFR = 0.065) is used as the polyolefin resin, polyvinyl butyral (PVB) is used as the polyvinyl acetal resin, and ethylene propylene is used as the rubber composition. The infrared spectroscopic spectrum of the test piece obtained by kneading propylene rubber (EPDM, "ESPRENE505", manufactured by Sumitomo Chemical Industries, Ltd.) at a weight ratio of HDPE: PVB: EPDM = 50: 25: 25 and injection molding. It is shown in FIG. In the above, the MFR of the resin base material (HDPE + EPDM) was 0.083 g / 10 minutes.

FIG 6 (A), the PVB ( "S-LEC B · K" BL-1, manufactured by Sekisui Chemical Co., Ltd.) having a molecular weight of 1.9 × 10 ⁴ test pieces were used, FIG. 6 (B), the molecular weight 1.1 × 10 ⁵ of PVB ( "S-LEC B · K" BH-3, manufactured by Sekisui Chemical Co., Ltd.) is an infrared spectrum of the test piece was used. In the figure, the solid line shows the infrared spectroscopic spectrum on the surface of the test piece, and the broken line shows the infrared spectroscopic spectrum on the cross section of the test piece.

In the resin base material system with an MFR of 0.083 g / 10 minutes, the cross section was compared regardless of whether the high molecular weight acetal resin (BH-3) or the low molecular weight acetal resin (BL-1) was used. It can be seen that more peaks (around 3300 cm ^-1 ) of the portion identified as the OH group appear on the surface.

[Comparative Example 3]
In FIG. 7, low density polyethylene (LDPE, “Novatec HD” LC525, manufactured by Nippon Polyethylene Co., Ltd., MFR = 8.4) was used as the polyolefin resin, and polyvinyl butyral (PVB) was used as the polyvinyl acetal resin, in terms of weight ratio. The infrared spectroscopic spectrum of the test piece obtained by kneading with LDPE: PVB = 75: 25 and injection molding is shown. Figure 7 (A) is, PVB ( "S-LEC B · K" BL-1, manufactured by Sekisui Chemical Co., Ltd.) having a molecular weight of 1.9 × 10 ⁴ test pieces were used, FIG. 7 (B), the molecular weight 1.1 × 10 ⁵ of PVB ( "S-LEC B · K" BH-3, manufactured by Sekisui Chemical Co., Ltd.) is an infrared spectrum of the test piece was used. In the figure, the solid line shows the infrared spectroscopic spectrum on the surface of the test piece, and the broken line shows the infrared spectroscopic spectrum on the cross section of the test piece.

In a low-density polyethylene (LC525) system with an MFR of 8.4 g / 10 min, when a low molecular weight acetal resin (BL-1) is used, the peak (3300 cm ^{-1) of the} portion identified as an OH group on the surface is used. It can be seen that (nearby) appears. On the other hand, when the high molecular weight acetal resin (BH-3) was used, the peak (around 3300 cm ^-1 ) of the portion identified as the OH group was more strongly observed in the cross section than in the surface, and the cross section data was further observed. There was a great deal of variation between them.

[Example 6]
Low-density polyethylene (LDPE, "Novatec HD" LC525, manufactured by Nippon Polyethylene Co., Ltd., MFR = 8.4) is used as the polyolefin resin, polyvinyl butyral (PVB) is used as the polyvinyl acetal resin, and ethylene propylene is used as the rubber composition. The infrared spectroscopic spectrum of the test piece obtained by kneading propylene rubber (EPDM, "ESPRENE505", manufactured by Sumitomo Chemical Industries, Ltd.) at a weight ratio of LDPE: PVB: EPDM = 50: 25: 25 and injection molding. It is shown in FIG. In the above, the MFR of the resin base material (LDPE + EPDM) was 1.6 g / 10 minutes.

FIG. 8 (A) is a molecular weight of 1.9 × 10 ⁴ of PVB ( "S-LEC B · K" BL-1, manufactured by Sekisui Chemical Co., Ltd.) A test piece was used, and FIG. 8 (B) has a molecular weight 1.1 × 10 ⁵ of PVB ( "S-LEC B · K" BH-3, manufactured by Sekisui Chemical Co., Ltd.) is an infrared spectrum of the test piece was used. In the figure, the solid line shows the infrared spectroscopic spectrum on the surface of the test piece, and the broken line shows the infrared spectroscopic spectrum on the cross section of the test piece.

In the resin base material system having an MFR of 1.6 g / 10 minutes, the cross section was compared regardless of whether the high molecular weight acetal resin (BH-3) or the low molecular weight acetal resin (BL-1) was used. It can be seen that more peaks (around 3300 cm ^-1 ) of the portion identified as the OH group appear on the surface. In this example, the same polyolefin resin (LC525) as in Comparative Example 3 is used. In the resin base material to which the rubber composition was not added, the MFR was 8.4 g / 10 minutes, but by adding rubber (EPDM) to this, the MFR was increased to 1.6 g / 10 minutes to increase the viscosity. It can be seen that the OH group is now expressed on the surface even when the high molecular weight acetal resin (BH-3) is used.

[Example 7]
Linear low density polyethylene (LLDPE) (“Sumicasene-L” FR152, manufactured by Sumitomo Chemical Co., Ltd., MFR = 1.8) is used as the polyolefin resin, and polyvinyl butyral (PVB) is used as the polyvinyl acetal resin, and the weight ratio is The infrared spectral spectrum of the test piece obtained by kneading with LLDPE: PVB = 75: 25 and injection molding is shown in FIG.

9 (A) is a molecular weight of 1.9 × 10 ⁴ of PVB ( "S-LEC B · K" BL-1, manufactured by Sekisui Chemical Co., Ltd.) test piece with, and FIG. 9 (B) has a molecular weight 1.1 × 10 ⁵ of PVB ( "S-LEC B · K" BH-3, manufactured by Sekisui Chemical Co., Ltd.) is an infrared spectrum of the test piece was used. In the figure, the solid line shows the infrared spectroscopic spectrum on the surface of the test piece, and the broken line shows the infrared spectroscopic spectrum on the cross section of the test piece.

In the resin base material system with an MFR of 1.8 g / 10 minutes, the cross section was compared regardless of whether the high molecular weight acetal resin (BH-3) or the low molecular weight acetal resin (BL-1) was used. It can be seen that more peaks (around 3300 cm ^-1 ) of the portion identified as the OH group appear on the surface. In particular, the tendency was more remarkable when the high molecular weight acetal resin was used.

[Example 8, Comparative Example 4]
The result of using polyvinyl butyral (PVB) to which a plasticizer was added as a polyvinyl acetal resin is shown.

FIG. 10 shows high molecular weight polypropylene (PP, “Novatec” EA9, manufactured by Nippon Polypro Co., Ltd., MFR = 0.52) and polypropylene (PP, homopolymer “Nobrene” Y501N, Sumitomo Chemical Industries, Ltd.) as polyolefin resins. , MFR = 13.1), polypropylene butyral (PVB) with a plasticizer added as a polyvinyl acetal resin, kneaded at a weight ratio of PP: PVB (including plasticizer) = 75:25 and injection molded. It is an infrared spectroscopic spectrum of the test piece obtained by the above. Figure 10 (A) is, MFR is 0.52 g / 10 min polypropylene, and, PVB ( "S-LEC B · K" BH-3, manufactured by Sekisui Chemical Co., Ltd.) having a molecular weight of 1.1 × 10 ⁵ plasticity to It is an infrared spectroscopic spectrum of a test piece using a plasticizer-added PVB in which the agent was mixed in a weight ratio of PVB: plasticizer = 3: 1 (Example 8). FIG. 10 (B), MFR is 13.1 g / 10 min polypropylene and, PVB ( "S-LEC B · K" BH-3, manufactured by Sekisui Chemical Co., Ltd.) having a molecular weight of 1.1 × 10 ⁵ to plasticizer It is an infrared spectroscopic spectrum of a test piece using a plasticizer-added PVB in which PVB: plasticizer = 3: 1 was blended in a weight ratio (Comparative Example 4). As the plasticizer, triethylene glycol-2-ethylhexanoate (G-260, manufactured by Sekisui Chemical Co., Ltd.) was used. Infrared spectroscopic spectra of the surface of the test piece are shown in FIGS. 10A and 10B.

The infrared spectroscopic spectrum (FIG. 10 (A)) of the surface of the test piece of Example 8 is an analysis result of the system of FIG. 1 (B) shown in Example 1 to which a plasticizer is added. There was no change in the situation. The infrared spectroscopic spectrum (FIG. 10 (B)) of the surface of the test piece of Comparative Example 4 is an analysis result of the system of FIG. 1 (D) shown in Comparative Example 1 with a plasticizer added. As in Example 8, no change was observed in the surface condition.

It can be seen that in the polypropylene (EA9) system having an MFR of 0.52 g / 10 minutes, a peak (around 3300 cm ^-1 ) of a portion identified as an OH group appears on the surface (Example 8).

On the other hand, in the polypropylene (Y501N) system having an MFR of 13.1 g / 10 minutes, the peak (around 3300 cm ^-1 ) of the portion identified as the OH group did not appear on the surface, and the cross section was the same as in Comparative Example 1. It is considered that it exists only in (Comparative Example 4).

As described above, by using a polyolefin resin having a melt flow rate of 4 g / 10 minutes or less, it is possible to add a polyvinyl acetal resin having a molecular weight exceeding 100,000 containing a plasticizer. Similar to Example 1, it was found that it is possible to expose more OH groups (hydrophilic components) to the surface to obtain a resin composition having good surface wettability.

The impact resistance of the test pieces of Example 8 and Comparative Example 4 and the polypropylene test pieces used in each system was measured at room temperature (23 ° C.). As a result, in the system of Example 8, the base material was 4.9 kJ / m ² , but the impact value of the test piece of Example 8 was 7.1 kJ / m ² , and the mechanical properties were improved. You can see that there is. On the other hand, in the system of Comparative Example 4, the impact value of polypropylene (“Nobren” Y501N) as a base material was 3.0 kJ / m ² , but the impact value of the test piece of Comparative Example 4 was 2.8 kJ /. It is m ² , and it can be seen that the mechanical properties are deteriorated.

According to this embodiment, the surface wettability and mechanical properties of the PVB resin of the interlayer film used for the windshield of an automobile and the PVB resin film left over as the scrap material to which the plasticizer is added, for example, Both have been shown to be effectively reusable as good resin compositions.

[Example 9]
The result of using polyvinyl butyral (PVB) to which a plasticizer and a radical initiator was added as a polyvinyl acetal resin is shown.

PVB ( "S-LEC B · K" BH-3, manufactured by Sekisui Chemical Co., Ltd.) having a molecular weight of 1.1 × 10 ^5, the plasticizer (G-260, manufactured by Sekisui Chemical Co., Ltd.), PVB weight ratio : 2 parts by weight of dicumylperoxide (“Parkmill D”, manufactured by Sekisui Chemical Co., Ltd.) was added as a radical initiator to 100 parts by weight of the mixture of plasticizer = 3: 1. High molecular weight polypropylene (PP, "Novatec" EA9, manufactured by Japan Polypropylene Corporation, MFR = 0.52) is used as the polyolefin resin, and the weight ratio is PP: PVB (including plasticizer) = 75:25. The test piece was obtained by kneading and injection molding.

When the impact resistance of the obtained test piece was measured at room temperature (23 ° C.), the impact value was 8.0 kJ / m ² , and the radical initiator obtained in Example 8 was added. It can be seen that the mechanical properties (impact resistance) are improved compared to the test piece without the test piece.

[Example 10]
The results of using polyvinyl butyral (PVB) to which a plasticizer and a radical initiator different from that of Example 9 are added as the polyvinyl acetal resin are shown.

PVB ( "S-LEC B · K" BH-3, manufactured by Sekisui Chemical Co., Ltd.) having a molecular weight of 1.1 × 10 ^5, the plasticizer (G-260, manufactured by Sekisui Chemical Co., Ltd.), PVB weight ratio : 2,5-Dimethyl-2,5-di (t-butylperoxy) hexane ("Kayahexa AD", Kayaku Akzo Co., Ltd.) as a radical initiator with respect to 100 parts by weight of a mixture of plasticizer = 3: 1. Manufactured by 2 parts by weight. High molecular weight polypropylene (PP, "Novatec" EA9, manufactured by Japan Polypropylene Corporation, MFR = 0.52) is used as the polyolefin resin, and the weight ratio is PP: PVB (including plasticizer) = 75:25. The test piece was obtained by kneading and injection molding.

When the impact resistance of the obtained test piece was measured at room temperature (23 ° C.), the impact value was 9.8 kJ / m ² , and the radical initiator obtained in Example 8 was added. It can be seen that the mechanical properties are improved compared to the test piece without the test piece.

[Example 11]
Molecular weight of 1.15 × 10 ⁵ PVB ( "S-LEC B · K" BH-A, manufactured by Sekisui Chemical Co., Ltd.), a plasticizer (G-260, manufactured by Sekisui Chemical Co., Ltd.), PVB weight ratio : 2 parts by weight of dicumylperoxide (“Parkmill D”, manufactured by Sekisui Chemical Co., Ltd.) was added as a radical initiator to 100 parts by weight of the mixture of plasticizer = 3: 1. High molecular weight polypropylene (PP, "Novatec" EA9, manufactured by Japan Polypropylene Corporation, MFR = 0.52) is used as the polyolefin resin, and the weight ratio is PP: PVB (including plasticizer) = 75:25. The test piece was obtained by kneading and injection molding.

The impact resistance of the obtained test piece was measured in a temperature range from room temperature (23 ° C.) to −40 ° C. The results are shown in FIG.

[Example 12]
To 100 parts by weight of the PVB interlayer film (including the plasticizer) of the process scrap, 2 parts by weight of dicumylperoxide (“Parkmill D”, manufactured by NOF CORPORATION) was added as a radical initiator. High molecular weight polypropylene (PP, "Novatec" EA9, manufactured by Japan Polypropylene Corporation, MFR = 0.52) is used as the polyolefin resin, and the weight ratio is PP: PVB (including plasticizer) = 75:25. The test piece was obtained by kneading and injection molding. The present process scrap is about 25% ester plasticizer (PVB: plasticizer = 3: 1), the molecular weight was achieved, each comprising a PVB of approximately 1.1 × 10 ^5.

The impact resistance of the obtained test piece was measured in a temperature range from room temperature (23 ° C.) to −40 ° C. The results are shown in FIG.

[Example 13]
2,5-Dimethyl-2,5-di (t-butylperoxy) hexane ("Kayahexa AD", chemical agent Axo) as a radical initiator with respect to 100 parts by weight of PVB interlayer film (including plasticizer) of process scraps. 2 parts by weight was added. High molecular weight polypropylene (PP, "Novatec" EA9, manufactured by Japan Polypropylene Corporation, MFR = 0.52) is used as the polyolefin resin, and the weight ratio is PP: PVB (including plasticizer) = 75:25. The test piece was obtained by kneading and injection molding.

The impact resistance of the obtained test piece was measured in a temperature range from room temperature (23 ° C.) to −40 ° C. The results are shown in FIG.

FIG. 11 shows the impact resistance measurement results of each test piece of Examples 11 to 13 and the impact value of polypropylene (“Novatec” EA9) as a base material at each temperature. It can be seen that each of the test pieces obtained in Examples 11 to 13 exceeds the impact value of the base material polypropylene (“Novatec” EA9) in all the measured temperature bands. In the actual recycling scene, the additives are not clear or the process scraps for multiple products are mixed. According to Examples 11 to 13, even if the type of PVB is different or unknown, the same tendency is observed for the impact value, and thus it is considered that the present invention can be effectively utilized in the recycling scene.

[Example 14 (A)]
Molecular weight of 1.15 × 10 ⁵ PVB ( "S-LEC B · K" BH-A, manufactured by Sekisui Chemical Co., Ltd.), a plasticizer (G-260, manufactured by Sekisui Chemical Co., Ltd.), PVB weight ratio : A mixture of plasticizer = 3: 1 was prepared. High molecular weight polypropylene (PP, "Novatec" EA9, manufactured by Japan Polypropylene Corporation, MFR = 0.52) is used as the polyolefin resin, and the weight ratio is PP: PVB (including plasticizer) = 75:25. The test piece was obtained by kneading and injection molding.

[Example 14 (B)] (Same conditions as in Example 11)
Molecular weight of 1.15 × 10 ⁵ PVB ( "S-LEC B · K" BH-A, manufactured by Sekisui Chemical Co., Ltd.), a plasticizer (G-260, manufactured by Sekisui Chemical Co., Ltd.), PVB weight ratio : 2 parts by weight of dicumylperoxide (“Parkmill D”, manufactured by Sekisui Chemical Co., Ltd.) was added as a radical initiator to 100 parts by weight of the mixture of plasticizer = 3: 1. High molecular weight polypropylene (PP, "Novatec" EA9, manufactured by Japan Polypropylene Corporation, MFR = 0.52) is used as the polyolefin resin, and the weight ratio is PP: PVB (including plasticizer) = 75:25. The test piece was obtained by kneading and injection molding.

[Example 15 (A)]
Molecular weight of 1.15 × 10 ⁵ PVB ( "S-LEC B · K" BH-A, manufactured by Sekisui Chemical Co., Ltd.), a plasticizer (G-260, manufactured by Sekisui Chemical Co., Ltd.), PVB weight ratio : A mixture of plasticizer = 3: 1 was prepared. Polypropylene (PP, "Novatec" FL203D, manufactured by Japan Polypropylene Corporation, MFR = 3.0) is used as the polyolefin resin, and kneaded so that the weight ratio is PP: PVB (including plasticizer) = 75:25. , Injection molding was performed to obtain a test piece.

[Example 15 (B)]
Molecular weight of 1.15 × 10 ⁵ PVB ( "S-LEC B · K" BH-A, manufactured by Sekisui Chemical Co., Ltd.), a plasticizer (G-260, manufactured by Sekisui Chemical Co., Ltd.), PVB weight ratio : 2 parts by weight of dicumylperoxide (“Parkmill D”, manufactured by Sekisui Chemical Co., Ltd.) was added as a radical initiator to 100 parts by weight of the mixture of plasticizer = 3: 1. Polypropylene (PP, "Novatec" FL203D, manufactured by Japan Polypropylene Corporation, MFR = 3.0) is used as the polyolefin resin, and kneaded so that the weight ratio is PP: PVB (including plasticizer) = 75:25. , Injection molding was performed to obtain a test piece.

[Comparative Example 5 (A)]
Molecular weight of 1.15 × 10 ⁵ PVB ( "S-LEC B · K" BH-A, manufactured by Sekisui Chemical Co., Ltd.), a plasticizer (G-260, manufactured by Sekisui Chemical Co., Ltd.), PVB weight ratio : A mixture of plasticizer = 3: 1 was prepared. Polypropylene (PP, "Novatec" FB3B, manufactured by Japan Polypropylene Corporation, MFR = 7.5) is used as the polyolefin resin, and kneaded so that the weight ratio is PP: PVB (including plasticizer) = 75:25. , Injection molding was performed to obtain a test piece.

[Comparative Example 5 (B)]
Molecular weight of 1.15 × 10 ⁵ PVB ( "S-LEC B · K" BH-A, manufactured by Sekisui Chemical Co., Ltd.), a plasticizer (G-260, manufactured by Sekisui Chemical Co., Ltd.), PVB weight ratio : 2 parts by weight of dicumylperoxide (“Parkmill D”, manufactured by Nichiyu Co., Ltd.) was added as a radical initiator to 100 parts by weight of the mixture of plasticizer = 3: 1. Polypropylene (PP, "Novatec" FB3B, manufactured by Japan Polypropylene Corporation, MFR = 7.5) is used as the polyolefin resin, and kneaded so that the weight ratio is PP: PVB (including plasticizer) = 75:25. , Injection molding was performed to obtain a test piece.

[Comparative Example 6 (A)]
Molecular weight of 1.15 × 10 ⁵ PVB ( "S-LEC B · K" BH-A, manufactured by Sekisui Chemical Co., Ltd.), a plasticizer (G-260, manufactured by Sekisui Chemical Co., Ltd.), PVB weight ratio : A mixture of plasticizer = 3: 1 was prepared. High molecular weight polypropylene (PP, homopolymer "Nobrene" Y501N, manufactured by Sumitomo Chemical Industries, Ltd., MFR = 13.1) is used as the polyolefin resin, and PP: PVB (including plasticizer) = 75: by weight. The mixture was kneaded to 25 and injection molded to obtain a test piece.

[Comparative Example 6 (B)]
Molecular weight of 1.15 × 10 ⁵ PVB ( "S-LEC B · K" BH-A, manufactured by Sekisui Chemical Co., Ltd.), a plasticizer (G-260, manufactured by Sekisui Chemical Co., Ltd.), PVB weight ratio : 2 parts by weight of dicumylperoxide (“Parkmill D”, manufactured by Sekisui Chemical Co., Ltd.) was added as a radical initiator to 100 parts by weight of the mixture of plasticizer = 3: 1. Polypropylene (PP, homopolymer "Nobrene" Y501N, manufactured by Sumitomo Chemical Industries, Ltd., MFR = 13.1) is used as the polyolefin resin, and the weight ratio is PP: PVB (including plasticizer) = 75:25. The test piece was obtained by kneading and injection molding.

Example 14 (A), Example 14 (B), Example 15 (A), Example 15 (B), Comparative Example 5 (A), Comparative Example 5 (B), Comparative Example 6 (A) and Comparison The impact value of the test piece obtained in Example 6 (B) was measured at room temperature (23 ° C.). In addition, the impact value of each PP (base material) used in each Example and Comparative Example was also measured. The results are shown in Table 1. In Example 14 (A), Example 14 (B), Example 15 (A) and Example 15 (B) using a resin base material having a melt flow rate of 4 g / 10 minutes or less, polyvinyl It can be seen that the impact resistance is improved as compared with the base material by blending butyral. On the other hand, in Comparative Example 5 (A), Comparative Example 5 (B), Comparative Example 6 (A) and Comparative Example 6 (B) using a resin base material having a melt flow rate of more than 4 g / 10 minutes, It can be seen that the impact resistance is lower than that of the base material by blending polyvinyl butyral.

Comparing Example 8 and Example 9 using a resin base material having a melt flow rate of 0.52 g / 10 minutes, the mechanical properties (impact resistance) were improved by adding the radical initiator. It was. In Examples 14 (A) and 14 (B) using the same resin base material, the addition of the radical initiator resulted in improvement in mechanical properties (impact resistance). On the other hand, in both Example 15 (A) and Example 15 (B) using the resin base material having a melt flow rate of 3.0 g / 10 minutes, the impact resistance was improved as compared with the resin base material. However, it can be seen that the effect of improving the mechanical properties (impact resistance) by adding the radical initiator has not been obtained. It is considered preferable that the melt flow rate of the resin base material is in the range of more than 0.5 and less than 3.0 from the viewpoint of impact resistance.

(Sample preparation method)
The method for preparing a sample for measurement used in the above is as follows. When there was a material that was not blended in each sample, the step was appropriately omitted and the following production method was applied.

First, as a preparation for each material, each material was processed into a shape (for example, a powder or granular material of several millimeter square) that could be put into the hopper of a twin-screw extruder.

Next, each material was mixed in advance before being charged into the hopper of the twin-screw extruder.

Next, each material processed as described above was kneaded using a twin-screw extruder. As the twin-screw extruder, "KZW15-45HG" (Φ = 15, L / D = 45) manufactured by Technobel Co., Ltd. was used. The operating conditions of the device were a screw rotation speed of 250 rpm and a feeder discharge rate of 15 g / min. The twin-screw extruder has six cylinders 1 to 6, and the set temperature of each cylinder is set to 180 ° C. for the first cylinder to the sixth cylinder and the die. Each material was heated and mixed with a twin-screw extruder, and the resin mixture was extruded from the die of the twin-screw extruder. The extruded mixture is in the form of strands (strings).

Subsequently, the strand-shaped resin mixture extruded from the die was cooled in a water tank and then pelletized with a pelletizer. Then, the obtained pellets were put in a bag and stirred to make the quality uniform.

Next, the obtained pellets were used to mold a test piece. Prior to molding the test piece, the pellets were heated and dried in a constant temperature bath set at 80 ° C. for about 2 hours.

Subsequently, using an injection molding machine, a multipurpose test piece (80 mm × 10 mm × 4 mm) conforming to JIS K7139 was prepared using the prepared pellet as a raw material. As the injection molding machine, "ES1000" manufactured by Nissei Resin Industry Co., Ltd. was used. As the operating conditions of the device, the cylinder temperature is set to be constant at 180 ° C., the injection speed is a predetermined speed of 5 to 40 mm / sec, the holding pressure is a predetermined pressure of 20 to 50 MPa, and the holding time is 15 seconds. The mold temperature was 40 ° C. and the cooling time was 15 to 40 seconds. When the two components of PVAcA and PP were mixed, the cylinder temperature was set to 195 ° C. for the head portion, 190 ° C. for the front portion, and 190 ° C. for the middle portion, respectively.

(Measurement method of impact resistance (Izod impact value))
A 2 mm notch was made in the produced multipurpose test piece using "No. 189 PNCA notch processing machine" manufactured by Yasuda Seiki Seisakusho Co., Ltd. Then, the Izod impact test was performed at a predetermined temperature using "No. 258-L-PC impact tester" manufactured by Yasuda Seiki Seisakusho Co., Ltd. The load of the hammer was 2.75 J, and the number of samples was N = 5.

As described above, the above-described embodiment is merely an example for carrying out the present invention. Therefore, the present invention is not limited to the above-described embodiment, and the above-described embodiment can be appropriately modified and implemented within a range that does not deviate from the gist thereof.

The resin composition of the present invention can be used for various purposes, and in particular, it can be suitably used for applications that require wettability. For example, it can be suitably used for pallets and containers of frozen warehouses, covers of metal frames constituting metal pallets, and the like. It may also be applied to battery separator materials. Furthermore, the resin composition of the present invention is recyclable. That is, since the hydrophilic component is present on the surface during molding, the same effect as before recycling can be obtained even after the product is crushed and recycled.

Claims (6)

Contains polyolefin-based resin and polyvinyl acetal resin (excluding polyvinyl formal resin)
The melt flow rate of the resin base material containing the polyolefin-based resin excluding the polyvinyl acetal resin is within the range of 0.01 g / 10 minutes or more and 4 g / 10 minutes or less.
The weight ratio of the content of the polyolefin resin to the content of the polyvinyl acetal resin is within the range of polyolefin resin: polyvinyl acetal resin = 99.9: 0.1: 0.1: 99.9. A resin composition characterized by. The resin composition according to claim 1, further comprising a rubber composition in the resin base material. The resin composition according to claim 2, wherein the rubber composition is at least one selected from the group consisting of ethylene propylene rubber, ethylene propylene diene rubber, butadiene rubber, styrene butadiene rubber, nitrile rubber, isoprene rubber, and a mixture thereof. object. The resin composition according to any one of claims 1 to 3, wherein the polyvinyl acetal resin is at least one selected from the group consisting of polyvinyl acetal acetal and polyvinyl butyral. The resin composition according to any one of claims 1 to 4, wherein the polyolefin-based resin is at least one selected from the group consisting of polypropylene resin and polyethylene resin. The resin composition according to any one of claims 1 to 5, further comprising a radical generator.