JPH0853549A - Liquid modifier-containing master batch and its production - Google Patents

Abstract

PURPOSE:To easily obtain the subject master batch easy to store for a long period, adequately presenting antifogging disposition in the form of an antifogging film and stretchability in the form of a stretch film, by blending and kneading a large amount of a liquid modifier with a polyolefin resin and an organic gelling agent. CONSTITUTION:(A) A liquid modifier (pref. a polybutene) and (B) an organic gelling agent (pref. 1,2-hydroxystearic acid) are mutually mixed and dissolved under heating, and the resultant mixture is added to (C) a polyolefin resin (pref. a low-density polyethylene resin) followed by conducting a kneading to obtain the objective master batch. In this case, the amount of the component A to be used is 120 pts.wt. based on 100 pts.wt. of the component C, and the weight ratio of B/A is (100:0.1) to (100:20).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a melt-kneading of a liquid modifier to a polyolefin resin (including a copolymer),
The present invention relates to a liquid modifier-containing masterbatch that does not cause stickiness due to bleeding by mixing an organic gelling agent and does not cause a blocking phenomenon of pellets, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, in resin molding, a masterbatch containing a large amount of various additives according to the purpose of use is diluted and used. For example, in the case of blending a surfactant to improve the wettability of the surface of the molded product such as antistatic effect and antifogging effect, and in the stretch film for the purpose of packaging the product, the adhesion to the product as a packaging agent Masterbatches have been used that incorporate tacky materials to improve. However, additives such as the above-mentioned surfactants and adhesive substances that are liquid at room temperature (hereinafter referred to as liquid modifier)
However, under the present circumstances, when the above liquid modifier is mixed in a carrier resin in a large amount, the kneading cannot be sufficiently performed. For example, if you try to mix a large amount of liquid surfactant into the resin using an extruder, the additive will not be kneaded into the resin in the cylinder, and the screw will spin off on the surface to precipitate and mix. Is impossible.

Similarly, when a liquid pressure-sensitive adhesive is kneaded into a resin, the raw material adheres to the feeder portion, making it difficult to produce a masterbatch. Moreover, if a large amount of the liquid modifier is blended, the liquid modifier will bleed on the surface of the resin pellets or powder immediately after the production or after a few days and the stickiness will become serious, blocking will occur between the resins, and in the hopper during dry blending. However, there is a problem in that bridging occurs and a predetermined amount cannot be blended, or the workability is remarkably deteriorated due to non-uniformity. For example, for forming a stretch film, it is necessary to add a large amount of polybutene, but stickiness is severe at the time of production, and therefore the amount is limited to a small amount. Therefore, in a masterbatch containing a liquid modifier such as a surfactant or a pressure-sensitive adhesive, the compounding amount is usually limited to 10% or less. This is because the masterbatch for coloring has a pigment content of up to about 50%, but conventionally, the masterbatch containing surfactants and adhesives has a remarkably low concentration. Not playing well.

[0004]

Therefore, the inventors of the present invention can easily manufacture a master batch containing a liquid modifier in which a large amount of the liquid modifier is blended in a thermoplastic resin, as compared with conventional products. Moreover, even when the masterbatch is stored for a long period of time, the liquid modifier does not bleed, and even when the masterbatch is packed in a bag and stored by stacking, there is no aggregation of pellets due to blocking, and the pellets are easy to handle and long-term storage. Is an easy one. Also, when a desired molded article is produced using the masterbatch, the desired effect, for example, a liquid modification that sufficiently exhibits antifog properties in an agricultural antifog film and stretch properties in a stretch film. A masterbatch containing a substance is provided.

[0005]

To achieve the above object, the present invention comprises three components: (A) a polyolefin resin, (B) a liquid modifier, and (C) an organic gelling agent. )
The ratio of 1 to 200 parts by weight of the component (B) to the component 100 parts by weight, and the ratio of the component (B) to the component (B) is (B):
(C) = A masterbatch containing a liquid modifier, which is prepared by mixing and kneading so as to be 100: 0.1 to 100: 20. Examples of the polyolefin resin as the component (A) of the present invention include polyethylene resins such as low density polyethylene, medium density polyethylene, and high density polyethylene, copolymers of ethylene and α olefin, polypropylene, ionomer,
EVA, EEA, polymethylpentene and the like can be mentioned.
These may be used alone or in combination of two or more.

Examples of the liquid modifier of the component (B) of the present invention include polybutene, fluid paraffin, process oil, DBP and DOA used as a plasticizer. Examples of the organic gelling agent as the component (C) of the present invention include metal soaps, 1,2-hydroxystearic acid, dibenzylidene sorbitol, amino acid derivatives and the like. In the present invention, the liquid modifier of the component (B) is blended at a ratio of 1 to 200 parts with respect to 100 parts by weight of the copolymer of the component (A) (hereinafter abbreviated as "parts"). At this time, if the content of the component (B) is less than 1 part, the commercial value of the masterbatch is poor, which is not preferable. On the other hand, if it is blended in an amount of more than 200 parts, the composition of the masterbatch loses its uniformity, and the productivity is not lowered during the production, which is not preferable from the viewpoint of cost.

At this time, the blending amount of the component (C) is (B)
It is based on the amount of the component used, (B) :( C) = 10
There are 0: 0.1 to 100: 20. The amount of component (C) used is (B):
When (C) is less than 100: 0.1, the component (B) is not uniformly dispersed in the component (A), and the productivity of the masterbatch is deteriorated, which is not preferable. The amount of the component (C) used is (B):
Even if more than (C) = 100: 20 is blended, the effect of blending the component (C) is not improved and the physical properties of the product of the present invention are deteriorated, which is not preferable.

In the production of the liquid modifying agent-containing masterbatch of the present invention, when the organic gelling agent is added to and mixed with the liquid modifying agent and heated and dissolved, the molecules of the organic gelling agent are gathered together during cooling. It is thought that it creates a network structure and wraps the liquid modifier in the bone.
The method for producing the masterbatch containing a liquid modifier of the present invention is as follows: (A) component, (B) component and (C) component are kneaded at the same time. A method in which two components of the component (C) are heated and dissolved and mixed, and then the polyolefin resin (A) is added thereto and kneaded may be used. If necessary, the liquid modifier-containing masterbatch of the present invention may contain other additives such as antioxidants, ultraviolet absorbers, lubricants and flame retardants in appropriate amounts. In addition, silica, calcium carbonate, talc, etc. may be arbitrarily mixed as a filler or a filler.

[0009]

EXAMPLES Examples and comparative examples will be described below. Example 1 (A) 100 parts linear low-density polyethylene resin (trade name: UA440 manufactured by Mitsubishi Kasei Co., Ltd.), (B) average molecular weight 1350
Polybutene resin (trade name: HV manufactured by Nippon Petrochemical Co., Ltd.
-300) 80 parts, and (B) as component (C): (C) = 10
0: 2.5 1,2-hydroxystearic acid 2 parts, above 3
The components were kneaded and extruded using a twin-screw extruder to produce a liquid modifier-containing masterbatch of the present invention. Example 2 (A) 100 parts of low-density polyethylene resin (Mitsui Petrochemical Co., Ltd. trade name: Mirason 402), (B) average molecular weight 1350
Polybutene resin (trade name: HV manufactured by Nippon Petrochemical Co., Ltd.
-300) 80 parts, (C) 1,2-hydroxystearic acid 2 parts,
The above three components are kneaded and extruded using a twin-screw extruder,
A liquid modifier-containing masterbatch of the present invention was produced.

Example 3 (A) 100 parts of linear low-density polyethylene resin (trade name: UA440, manufactured by Mitsubishi Kasei Co., Ltd.), (B) average molecular weight 1350
Polybutene resin (trade name: HV manufactured by Nippon Petrochemical Co., Ltd.
-300) 80 parts, and (B) as component (C): (C) = 10
0.5 parts of dibenzylidene sorbitol at 0: 0.625, and the above three components were kneaded and extruded using a twin-screw extruder to produce a liquid modifier-containing masterbatch of the present invention. Example 4 (A) 100 parts of low-density polyethylene resin (Mitsui Petrochemical Co., Ltd. trade name: Mirason 402), (B) Fluid Paraffin (Nippon Petrochemical Co., Ltd. trade name: White 350) 60
And 0.6 parts of benzylidene sorbitol so that (B) :( C) = 100: 1 as component (C), the above three components are kneaded and extruded using a twin-screw extruder, and the liquid modification of the present invention is performed. An agent-containing masterbatch was produced.

Example 5 (B) 100 parts of a polybutene resin having an average molecular weight of 1350 (trade name: HV-300 manufactured by Nippon Petrochemical Co., Ltd.) and (C) 3 parts of 1,2-hydroxystearic acid were heated and melt mixed. A mixture having a viscosity at 40 ° C of 160,000 pa · s was obtained. 100 parts of the mixture and 120 parts of (A) linear low-density polyethylene resin (trade name: UA440 manufactured by Mitsubishi Kasei Kogyo Co., Ltd.) are kneaded and extruded using a twin-screw extruder to obtain the liquid modifier of the present invention. A containing masterbatch was produced. Example 6 (B) 100 parts of a polybutene resin having an average molecular weight of 1350 (trade name: HV-300 manufactured by Nippon Petrochemical Co., Ltd.) and (C) 0.6 part of dibenzylidene sorbitol were heated and melt mixed to obtain a viscosity of 120,000 at 40 ° C. A mixture of pa · s was obtained. The mixture 60
Parts and (A) 120 parts of linear low-density polyethylene resin (product of Mitsubishi Kasei Kogyo Co., Ltd .: UA440) are kneaded and extruded using a twin-screw extruder to obtain a masterbatch containing the liquid modifier of the present invention. Manufactured.

Example 7 (B) 100 parts of fluid paraffin (trade name: white 350 manufactured by Nippon Petrochemical Co., Ltd.) and (C) 1.0 part of dibenzylidene sorbitol were heated and melt mixed to obtain a viscosity at 40 ° C. of 80,000 pa. A mixture of s was obtained. 60 parts of the mixture and (A) low-density polyethylene resin (product of Mitsui Petrochemical Co., Ltd .:
100 parts of Mirason 402) was kneaded and extruded using a twin-screw extruder to produce a liquid modifier-containing masterbatch of the present invention. Comparative Example 1 (A) 100 parts of linear low-density polyethylene resin (trade name: UA440 manufactured by Mitsubishi Kasei Co., Ltd.) and (B) average molecular weight 13
50 polybutene resins (trade name of Nippon Petrochemical Co., Ltd .:
HV-300) 80 parts, kneading the above two components using a twin-screw extruder
It was extruded to prepare a liquid modifier-containing masterbatch.

Comparative Example 2 (A) 100 parts of low-density polyethylene resin (Mitsui Petrochemical Co., Ltd., trade name: Mirason 402) and (B) liquid paraffin (Japan Petrochemical Co., Ltd., trade name: White 350) 60
Parts, the above two components were kneaded and extruded using a twin-screw extruder to produce a liquid modifier-containing masterbatch. Comparative Example 3 (A) 100 parts of linear low-density polyethylene resin (trade name: UA440 manufactured by Mitsubishi Kasei Co., Ltd.) and (B) average molecular weight 13
50 polybutene resins (trade name of Nippon Petrochemical Co., Ltd .:
HV-300) 80 parts, and (B) as component (C): (C) =
18 parts of dibenzylidene sorbitol of 100: 22.5, and the above three components were kneaded and extruded using a twin-screw extruder to produce a masterbatch containing a liquid modifier. Comparative Example 4 (A) 100 parts linear low-density polyethylene resin (trade name: UA440 manufactured by Mitsubishi Kasei Co., Ltd.), (B) average molecular weight 1350
Polybutene resin (trade name: HV manufactured by Nippon Petrochemical Co., Ltd.
-300) 80 parts, and (B) as component (C): (C) = 10
0.01 parts of 1,2-hydroxystearic acid having a ratio of 0: 0.125, and the above three components were kneaded and extruded using a twin-screw extruder to produce a masterbatch containing a liquid modifier.

Comparative Example 5 (A) 100 parts of linear low-density polyethylene resin (trade name: UA440 manufactured by Mitsubishi Kasei Co., Ltd.), (B) average molecular weight 1350
Polybutene resin (trade name: HV manufactured by Nippon Petrochemical Co., Ltd.
-300) 80 parts, and (B) as component (C): (C) = 10
30 parts of 1,2-hydroxystearic acid (0: 37.5) and the above three components were kneaded and extruded using a twin-screw extruder to produce a liquid modifier-containing masterbatch. Comparative Example 6 (A) 100 parts linear low-density polyethylene resin (trade name: UA440 manufactured by Mitsubishi Kasei Co., Ltd.), (B) average molecular weight 1350
Polybutene resin (trade name: HV manufactured by Nippon Petrochemical Co., Ltd.
-300) 250 parts, and as component (C) (B): (C) = 1
5 parts of dibenzylidene sorbitol to be 00: 2 and the above three components were kneaded and extruded using a twin-screw extruder to produce a masterbatch containing a liquid modifier.

Comparative Example 7 (A) 100 parts of linear low-density polyethylene resin (trade name: UA440 manufactured by Mitsubishi Kasei Co., Ltd.), (B) average molecular weight 1350
Polybutene resin (trade name: HV manufactured by Nippon Petrochemical Co., Ltd.
-300) 0.9 parts, and (C) as component (B): (C) = 1
0.027 parts of dibenzylidene sorbitol at 00: 3 and the above three components were kneaded and extruded using a twin-screw extruder to produce a masterbatch containing a liquid modifier. As described above, the test pieces obtained in Examples 1 to 7 and Comparative Examples 1 to 7 were evaluated by the following method, and the measurement results are shown.

[Table 1] Shown in a. Manufacturability (Manufacturability of Masterbatch) The evaluation at the time of manufacturing the masterbatch was evaluated according to the following criteria. ○: Good workability during extrusion. ×: Workability during extrusion is poor.

B. Pellet Blocking Test Cylindrical pellets (average diameter 3 mm, average length 3 mm) obtained in each of the examples and comparative examples were filled in an acrylic pipe having an inner diameter of 63 mm and a height of 100 mm, and a load of 45 kg was applied at 60 ° C. for 3 days. After standing for one day, the mixture was allowed to cool to room temperature, then the load and the pipe were removed, and the state of the pellet was investigated. ○ …… The pellets are not sticky and can be easily loosened. × …… Pellets are sticky and solid. c. Film Properties The liquid modifier-containing master batches obtained in each of the examples and comparative examples were diluted and the appearance and performance when film-formed were evaluated. ○ …… Meets the required performance in terms of properties and characteristics. × …… The film has a poor appearance or does not meet the required performance.

[0017]

The product of the present invention is (B) a liquid modifier and (C)
By adding an organic gelling agent and melt-kneading, (B)
By suppressing the bleeding of the components to the surface, it is easy to handle when manufacturing a masterbatch and when forming stretch film, agricultural anti-fog film, etc., and contains a liquid modifier with excellent workability. It provides a masterbatch. Specifically, since the liquid modifier does not bleed on the surface during masterbatch production and there is little blocking or slippage between the pellets, it becomes sticky when mixed with the (A) polyolefin resin. It became possible to manufacture masterbatch pellets with excellent uniform dispersion without slipping.

Claims (2)

[Claims] 1. A three-component composition comprising (A) a polyolefin resin, (B) a liquid modifier, and (C) an organic gelling agent,
The ratio of 1 to 200 parts by weight of the (B) component and (B) component as the (C) component to 100 parts by weight of the (A) component is (B) :( C) = 100: 0.1 to 100: 20. A masterbatch containing a liquid modifier, which is prepared by mixing and kneading so that 2. The blending ratio according to claim 1,
(B) A liquid modifier and (C) an organic gelling agent are heated and dissolved and mixed, and then (A) a polyolefin resin is added and kneaded to the mixture, which is a method for producing a master batch containing a liquid modifier.