TWI509010B - Thermoplastic resin composition for cleaning - Google Patents

Description

Thermoplastic resin composition for cleaning

The present invention relates to a thermoplastic resin composition for cleaning which is used for cleaning the inside of a thermoplastic resin molding processing machine such as an extruder or an injection molding machine.

Patent Document 1 (JP-A-2009-107160) discloses a detergent composition for a molding machine, which comprises a thermoplastic resin, a second thermoplastic resin incompatible with the thermoplastic resin, and a fluorinated polymer; A cleaning agent for a molding machine containing a styrene resin and a propylene resin is disclosed in JP-A-2005-219398. The phase separation of these two resins is remarkable, and there is no sufficient function as a detergent.

A cleaning agent for a molding machine in which a graft polymer composed of an olefin polymer and a styrene polymer is mixed with a styrene thermoplastic resin is disclosed in Japanese Laid-Open Patent Publication No. Hei 05-42547. A cleaning agent for a molding machine, which is a mixture of a styrene-acrylonitrile resin and a polyethylene-based ultra-polymer, and an olefin-based polymer and a benzene, is disclosed in Japanese Laid-Open Patent Publication No. Hei 08-155969. A graft polymer composed of a vinyl polymer. In the case where the molding resin under the detergent is an olefin-based resin, the effect of replacement is easy. However, the substitution property or the detergency of the polypropylene resin itself is not sufficiently satisfied.

In the resin composition for cleaning, a polyolefin resin, a polymethyl methacrylate, a neutral salt of an organic sulfonic acid, a basic magnesium carbonate, and the like are disclosed in the patent document 5 (JP-A- 03-207734). Magnesium hydroxide, aluminum hydroxide, zinc carbonate or a mixture of two or more of these, but the detergency is insufficient.

A thermoplastic resin composition for cleaning, which contains a specific methacrylic acid in a thermoplastic resin, is disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. Ester-styrene copolymers and specific surfactants. A resin composition for cleaning comprising a polyolefin resin, an acrylic copolymer, a neutral salt of an organic sulfonic acid, magnesium carbonate, magnesium hydroxide, etc., is disclosed in JP-A-4-246443. a mixture. These compositions are all insufficient in detergency.

Patent Document 8 discloses a resin composition for cleaning, which comprises an acrylic copolymer, an organic sulfonate, and inorganic particles in a polyolefin resin, but has insufficient detergency.

In the olefin-based thermoplastic resin, an olefin-based thermoplastic resin containing an unsaturated group-containing carboxylic acid derivative-modified olefin-based resin and a polymer are disclosed in JP-A-2007-176765. An alkylene oxide or a polyolefin-based diol surfactant or a metal salt of a fatty acid, but the detergency is insufficient.

An object of the present invention is to provide a thermoplastic resin composition for cleaning which is excellent in detergency after washing a thermoplastic resin molding machine such as an extruder or an injection molding machine, and is cleaned after washing. When polypropylene is formed, the replacement of polypropylene is easy.

The present invention provides a thermoplastic resin composition for cleaning comprising 0 to 50 parts by mass of (B) per 100 parts by mass of the (A) polypropylene, which is incompatible with the component (A). The molten thermoplastic resin is 0.5 to 50 parts by mass of (C), which is a thermoplastic resin for dissolving the component (A) and the component (B), and 0.5 to 15 parts by mass of (D). One or more kinds selected from the anionic surfactants and one or more surfactant mixtures selected from the nonionic surfactants are contained.

The present invention provides a use of the above thermoplastic resin composition for washing a thermoplastic resin molding processing machine.

The thermoplastic resin composition for cleaning according to the present invention has good detergency when cleaning the inside of a thermoplastic resin molding machine such as an extruder or an injection molding machine, and particularly after washing, polypropylene is subsequently used. At the time of molding, the replacement of polypropylene is easy.

<(A) component>

The polypropylene resin of the component (A) may be a homopolymer or a block copolymer. The block copolymer is preferably a block copolymer of propylene and ethylene.

The polypropylene resin of the component (A) can be a mixture of a homopolymer and a block copolymer, and the mass of the homopolymer and the block copolymer is preferably from 1/9 to 9/1, more preferably 1/9. 4/6.

<(B) component>

The thermoplastic resin in which the component (B) is incompatible with the polypropylene resin of the component (A) is not an essential component in the present invention, but is a component which improves the detergency due to the inclusion.

The thermoplastic resin of the component (B) is preferably one or more selected from the group consisting of polymers or copolymers containing at least one of methyl methacrylate and styrene. The polymer or the copolymer may be one or more selected from the group consisting of AS resin, MS resin, methyl methacrylate-maleic anhydride-styrene copolymer, and PMMA resin.

The content ratio of the thermoplastic resin of the component (B) is 0 to 50 parts by mass, preferably 3 to 40 parts by mass, more preferably 5 to 30 parts by mass, per 100 parts by mass of the component (A).

<(C) component>

The thermoplastic resin of the component (C) is a component for dissolving the polypropylene resin of the component (A) and the thermoplastic resin of the component (B). In addition, even if the component (B) is not contained, since the component (C) itself has a cleaning effect, the component (C) is contained to improve the detergency of the composition.

The thermoplastic resin of the component (C) is preferably a graft copolymer containing a polymer or a copolymer containing at least one of (meth) acrylate and styrene as a main chain of an olefin resin. One or more selected ones. Here, (meth) acrylate means acrylate or methacrylate.

As the graft copolymer, a graft copolymer containing a polymer or a copolymer containing at least one of (meth) acrylate and styrene is preferably grafted with an olefin resin as a main chain. In this case, the olefin-based resin of the main chain is preferably a PP resin, an LDPE resin or an EEA resin, and the grafted polymer or copolymer is preferably an AS resin or a (meth)acrylic resin.

The content ratio of the thermoplastic resin of the component (C) is 0.5 to 50 parts by mass, preferably 2 to 30 parts by mass, more preferably 3 to 20 parts by mass, per 100 parts by mass of the component (A).

<(D) component>

The component (D) contains one or more kinds selected from the anionic surfactants and one or more surfactant mixtures selected from the nonionic surfactants.

The anionic surfactant is one or two or more surfactants selected from the group consisting of an aliphatic surfactant and an aromatic surfactant.

The aliphatic surfactant is preferably an alkanesulfonic acid sodium salt or an α-olefinsulfonic acid sodium salt; and as the aromatic surfactant, an alkylbenzenesulfonate sodium salt is preferred.

When the content ratio (mass basis) of the mixture of the aliphatic surfactant and the aromatic surfactant is used, the aliphatic surfactant/aromatic surfactant is preferably from 1/10 to 10/1. The range is preferably in the range of 1/6 to 6/1, and particularly preferably in the range of 1/3 to 3/1.

The nonionic surfactant is, for example, an oxyethylene chain surfactant, a sorbitan ester type surfactant, a glycericeride system (glycerol (mono-di) fatty acid ester) surfactant, 12-hydroxyl group. Selected among stearates, propylene glycol fatty acid esters, sucrose fatty acid esters, alkyl glyceryl ethers, alkyl glycosides, and the like.

Among these, one or more selected from the group consisting of sorbitan fatty acid ester, glycerin fatty acid ester, and 12-hydroxystearic acid ester are preferable.

In the component (D), the content ratio of the anionic surfactant to the nonionic surfactant is from 20 to 70% by mass, preferably from 25 to 70% by mass, more preferably from 30 to 65% by mass, based on the anionic surfactant. Further, the total amount of the nonionic surfactants was 100% by mass of the remaining portion.

The content ratio of the surfactant mixture of the component (D) is 0.5 to 15 parts by mass, preferably 1 to 10 parts by mass, more preferably 2 to 10 parts by mass per 100 parts by mass of the component (A). .

<(E) component>

The composition of the present invention may further contain a metal salt of 12-hydroxystearic acid as the component (E).

The metal salt of 12-hydroxystearic acid may be, for example, a zinc salt, an aluminum salt, a calcium salt or a magnesium salt, but a zinc salt or an aluminum salt is preferred from the viewpoint of further improving the detergency.

<Other ingredients>

The composition of the present invention may further contain an inorganic filler. In addition to the known glass fiber or the metal fiber, the slag, the iron steel slag, or the pulverized material or the artificial mineral fiber described in JP-A-2006-257297 can be used, and the fiber can be used. Shaped, non-fibrous (powdered, granulated, pulverized, etc.).

The composition of the present invention may further contain an olefinic diol fatty acid ester, an organic phosphorus compound, a polyhydric alcohol or a metal soap described in JP-A-2006-257297.

The composition of the present invention is prepared by mixing the above components in a mixer such as a Henschel mixer, a Tumbler blender, a kneader, or the like, and kneading the mixture by an extruder. The heating roll and the Bamburi mixer are melt-kneaded and manufactured.

Although the cleaning means for improving the detergency using the composition of the present invention is not known, it is judged that the polypropylene resin having the component (A) having no polar group is added to be incompatible with the polypropylene resin and has polarity ( The resin of the component B) is further stabilized by blending the component (C) which is a compatibilizing agent of the components (A) and (B), and the polypropylene resin of the component (A) can be substantially polar. The base has the same effect, so the detergency is increased. Further, even when the component (B) is not contained, high detergency can be obtained by combining the components of the components (A), (C), and (D).

In the composition of the present invention, the polypropylene resin based on the component (A) is used as a base component, and the polypropylene resin is easily replaced after washing, and is suitable as an extruder or an injection molding machine used for molding polypropylene. For the cleaning of thermoplastic resin molding machines.

Example

Examples and comparative examples

The components of the composition shown in Table 1 were mixed in a tubular mixer, and then melt-kneaded by an extruder to obtain a pellet-shaped thermoplastic resin composition. Using these compositions, a washing test was carried out by the following method. The results are shown in Table 1.

In the injection molding machine ("SH100" manufactured by Sumitomo Heavy Industries, Ltd.; cylinder temperature: 230 °C), the black resin of AS resin (Sesvian-N 080SF, manufactured by DAICEL Polymer Co., Ltd.), which is used as a resin, is used. Coloring product (carbon black concentration 2%) 1kg. Then, each composition of Table 1 was flowed in until the disappearance of black, and the detergency was evaluated by the amount of use of the composition.

As is apparent from comparison between the examples and the comparative examples, the composition of the examples was greatly improved in detergency.

From the comparison of Examples 5 and 6 with Examples 10 and 11, it is known that, as compared with the case of using calcium salt of 12-hydroxystearic acid or magnesium salt, zinc salt of 12-hydroxystearic acid or aluminum salt is used as ( The case of the component E) is high in detergency.

(Ingredients shown in Table 1)

<(A) component>

‧Polypropylene: Prime Polypro E111G (Homopolymer, MFR 0.5) manufactured by PRIME Polymer Co., Ltd.

<(B) component>

‧AS resin: Sesvian-N 080SF manufactured by DAICEL Polymer Co., Ltd.

‧MS resin: Sesvian-MAS30 manufactured by DAICEL Polymer Co., Ltd.

<(C) component>

‧PP-g-AS: graft copolymer with main chain of pp and side chain AS (Modiper A3400 by Nippon Oil Co., Ltd.)

‧EEA-g-AS: graft copolymer with main chain EEA and side chain AS (Modiper A5400 manufactured by Nippon Oil Co., Ltd.)

‧EEA-g-P(BA/MMA): a graft copolymer of a copolymer having a main chain of EEA and a side chain of butyl acrylate/methyl acrylate (Modiper A5300 manufactured by Nippon Oil Co., Ltd.)

<(D) component>

‧Anionic surfactant 1: sodium olefin sulfonate

‧Non-ionic surfactant 1: glycerin monobehenate

‧Nonionic Surfactant 2: Sorbitan Tribehenate

‧Nonionic surfactant 3: Glycerol 12-hydroxy monostearate

Claims (10)

A thermoplastic resin composition for cleaning, comprising: 10 to 50 parts by mass of (C) copolymer based on 100 parts by mass of (A) polypropylene, which is mainly composed of an olefin resin; a graft copolymer of a styrene-containing polymer or copolymer, the olefin-based resin-based polypropylene, a low-density polyethylene resin (LDPE) or an ethylene-ethyl acrylate resin (EEA); and 0.5 to 15 parts by mass The (D) surfactant mixture contains one or more selected from the group consisting of anionic surfactants and one or more selected from the group consisting of nonionic surfactants. A thermoplastic resin composition for cleaning comprising 3 to 50 parts by mass of (B), relative to 100 parts by mass of (A) polypropylene, which is incompatible with (A) component Resin, 0.5 to 50 parts by mass of (C), which is a thermoplastic resin for dissolving (A) component and (B) component, and 0.5 to 15 parts by mass of (D), which contains an anionic interface One or more selected from the active agents and one or more surfactant mixtures selected from the nonionic surfactants. The thermoplastic resin composition for cleaning according to the second aspect of the patent application, wherein the thermoplastic resin of the component (B) is an AS resin, an MS resin, a methyl methacrylate-maleic anhydride-styrene copolymer, and One or more selected from PMMA resins. The composition of the thermoplastic resin for cleaning according to item 2 of the patent application scope The thermoplastic resin of the component (C) is a graft copolymer containing a polymer or a copolymer containing (meth) acrylate or styrene, which is a main chain of an olefin resin, and the olefin resin is a olefin resin. Polypropylene, low density polyethylene resin (LDPE) or ethylene-ethyl acrylate resin (EEA), polymer or copolymer containing (meth) acrylate or styrene (meth) acrylate resin, AS resin Or a copolymer of butyl acrylate-methyl methacrylate. The thermoplastic resin composition for cleaning according to any one of claims 1 to 4, wherein the nonionic surfactant of the component (D) is a sorbitan fatty acid ester, a glycerin fatty acid ester, and 12 The selected one is -hydroxystearate. The thermoplastic resin composition for cleaning according to any one of claims 1 to 4, which further comprises (E) a metal salt of 12-hydroxystearic acid. A thermoplastic resin composition for cleaning according to item 5 of the patent application, which further contains (E) a metal salt of 12-hydroxystearic acid. A thermoplastic resin composition for cleaning according to the sixth aspect of the invention, wherein the metal salt of the 12-hydroxystearic acid of the component (E) is a zinc salt or an aluminum salt. The thermoplastic resin composition for cleaning according to the seventh aspect of the invention, wherein the metal salt of the 12-hydroxystearic acid of the component (E) is a zinc salt or an aluminum salt. A use of the thermoplastic resin composition according to any one of claims 1 to 9 for washing a thermoplastic resin molding machine.