KR100524092B1 - Polyolefin films, compositions and useful resins for these and related manufacturing methods - Google Patents

Abstract

The present invention relates to a mixture of a first component selected from talc and a second component selected from feldspar, nepheline and nepheline syenite, wherein the ratio of the first component to the second component is improved. It characterized in that to provide. The present invention also relates to antiblocking agents made from such mixtures. Such mixtures provide desirable optical properties when used in polyolefin films. The present invention also relates to a polyolefin resin composition comprising such a mixture and a film made thereof.

Description

Polyolefin Films, Compositions and Resins Useful in These and Related Processes

FIELD OF THE INVENTION The present invention relates to polyolefin resin compositions, precursor materials used therein, and films made therefrom, and in particular, to the use of talc and feldspar, nepheline and / or nepheline syenite combinations. It is about.

The present invention relates to a polyolefin resin composition comprising an antiblocking agent having a low polishing degree and required for the production of a transparent film having excellent antiblocking performance.

Polyolefin films are widely used for packaging materials around the world and are increasingly replacing conventional materials such as paper. The high transparency polyolefin film is visible so you can check the package contents. However, when plastic films are made, there are "blockings" where two or more film contact layers tend to stick to each other, or separate the film, open the bag, or make it difficult to find the end of the roll.

It is commercially required to add inorganic mineral fillers to polyolefin films to reduce blocking. Films made from resins containing antiblocking fillers have a rougher surface that reduces intimate contact between the film layers and reduces blocking, so that the term "blocking agent" applies to such fillers.

Not all inorganic fillers are useful as antiblocking agents, and some effective antiblocking agents have other problems that limit commercialization (high cost, high degree of polishing, adverse effects on optical properties, and health hazards). In order to reduce the blocking strength to the desired level, the smallest amount of antiblocking agent should be added while minimizing adverse effects on the optical properties of the film and other considerations such as wear on the processing equipment should be considered.

Diatomaceous earth is a widely used and effective antiblocking agent but has the following adverse effect: the film becomes cloudy, low in transparency, very abrasive and quite expensive. Talc is also widely used as an effective antiblocking agent in polyolefin compositions. Advantages of talc compared to diatomaceous earth are low cost, good film transparency and very low polishing. However, the film may also become cloudy, which may be good for other applications, but not suitable for high transparency packaging applications. Although stone seraphite or feldspar is considered an antiblocking agent for high transparency films because the reflective optical index is close to polyethylene, they are relatively ineffective in reducing blocking and have a very high degree of polishing.

The degree of polishing of the inorganic antiblocking agent is considered for several reasons. High abrasive blocking agents will contribute to rapid device wear in mixing and processing equipment. When wear reaches the point where the device space changes to critical areas, it can adversely affect the dispersion and yield of additives in the resin. In such a case, there is a problem that the quality of the product is affected and the manufacturing cost is increased, and in particular, if the device needs to be repaired, a new part must be purchased to replace the worn part of the device. In addition, wear of the device introduces metal contaminants into the plastic product, which has a fatal effect on product stability or color or both. For this reason, it is preferable that an antiblocking agent is low in polishing degree. Various attempts have been made by other inventors to solve the problem of harmonizing polyethylene film anti-blocking and clouding properties, but no one needs to consider the transparency and anti-blocking wear and cost of the film (all of which need to be considered in realizing commercialized products). It does not address the additional consideration of screens. In the present context, no cost effective antiblocking formulations for high transparency polyolefin films with low antiblocking agents have yet been found.

The present invention provides a method for treating talc with a component selected from the group consisting of feldspar, lower stone and sile rock, in which the ratio of talc to components selected from the group consisting of feldspar, lower stone and selenite rocks provides a significantly lower polishing degree than would be expected from the mixing law. Relates to a mixture. The present invention also provides an antiblocking effect of talc to a component selected from the group consisting of feldspar, sediment and sedimentary islet rock, wherein the talc is composed of An antiblocking agent made of a mixture. When the antiblocking agent is used in the polyolefin film, the optical properties are not significantly lowered.

The present invention also provides a significantly lower polishing rate than that foreseen from the law of mixing for a component selected from the group consisting of feldspar, lower stone and lower stone islands, and the component selected from the group consisting of feldspar, river stone and lower stone islands. Talc relates to a mixture of talc and a component selected from the group consisting of feldspar, sediment and sedimentary islet rock that provide a blocking prevention effect significantly greater than each component.

The present invention also provides a significantly lower polishing rate than that foreseen from the law of mixing for a component selected from the group consisting of feldspar, lower stone and lower stone islands, and the component selected from the group consisting of feldspar, river stone and lower stone islands. The ratio of talc to is directed to a polyolefin resin composition that provides a significantly greater antiblocking action than each component.

The present invention also relates to a polyolefin film composed of a polyolefin resin composition, which film can be made of the above components having a significantly lower polishing degree than predicted from the mixing law, and exhibits a significantly greater antiblocking action than each component. Can have

An advantage of the present invention is that the mixtures and polyolefin resin compositions of the present invention can be used to produce films with good antiblocking and optical properties (blur and transparency). The precursor mixtures also have low polishing. The combined mixtures exhibit significantly higher synergies than would be expected when antiblocking activity alone was, while maintaining the optical properties and low polishing.

Related Technology

Japanese Laid-Open Patent Publication No. 60-49047 by Matsumoto et al. Discloses a method of using a polyolefin resin composition containing a polyolefin resin, a finely powdered organic filler, an unsaturated fatty acid amide, and a mixed fatty acid polyester.

US Patent No. 5,346,944 to Hayashida et al. Discloses polyolefin resins, including antiblocking agents and optional antistatic agents, antifogants and antioxidants.

One example of the present invention relates to a mixture of talc and a component selected from the group consisting of feldspar, lower stone and lower stone islands, wherein the ratio of talc to components selected from the group consisting of feldspar, lower stone and lower stone islands is expected from the mixing law. To provide significantly lower polishing levels.

Preferably, the degree of polishing is about 80% or less of what is expected in the mixing law, and more preferably about 50% or less of what is expected in the mixing law.

This mixture has polyolefin resin compositions, and films prepared from polyolefin resin compositions and other types of products, such as sheets, castings and castings, useful as precursor materials. Polyolefins suitable for the present invention may be transparent crystalline and may be other polyolefins moldable into self-supporting films. Non-limiting examples include crystalline homopolymers of C _2-12 α-olefins or mixtures of two or more crystalline hollow copolymers or ethylene-vinylacetate copolymers with other resins. Examples of the polyolefin resin include high density polyethylene, low density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer, poly-1-butene, ethylene-vinylacetate copolymer, and the like, and low and medium density polyethylenes. Other examples include random or block copolymers of polyethylene, polypropylene, poly-γ-methylpentene-1, and ethylene-propylene, and ethylene-propylene-hexane copolymers. Among these, particular preference is given to copolymers of ethylene propylene and one or two selected from butene-1, 4-methylpentene-1, and octene-1 (so-called LLDPE). There is no restriction | limiting in the method of manufacturing the polyolefin resin of this invention. For example, it can manufacture by ionic polymerization or radical polymerization. Examples of polyolefin resins obtainable by ion polymerization include homopolymers such as polyethylene, polypropylene, polybutene-1, and poly-4-methylpentene and copolymers obtained by copolymerization of ethylene and α-olefins. Α-olefins include α-olefins having 3 to 18 carbon atoms, such as propylene, butene-1, hexene-1, octene-1, decene-1 and octadecene-1; It can be used in two or more forms. Other examples include propylene copolymers such as copolymers of propylene and butene-1. Examples of polyolefin resins obtainable by radical polymerization are copolymerized resins obtained by copolymerization of polyethylene or ethylene with radically polymerizable monomers. Examples of radically polymerizable monomers include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid esters, anhydrides thereof, and vinyl esters such as vinyl acetate. Specific examples of unsaturated carboxylic acid esters include ethyl acrylate, methyl methacrylate, and glycidyl methacrylate. These radically polymerizable monomers may be used individually or in two or more forms.

In the present invention, talc is selected for use in the polyolefin material produced. Typical talc has a monoclinic crystal structure, specific gravity of 2.6 to 2.8, and an empirical formula of Mg ₃ Si ₄ O ₁₀ (OH) ₂ .

Preferably, the average particle size of the talc used is from 0.1 to 10 microns.

In the present invention, the other components are selected from feldspar, lower and lower island ileus, or mixtures thereof. These materials are known in the art and include "Minerals and Rocks", The New Encyclopedic Britannica, Vol 24, pp. Conveniently prescribed by 151-157, 175-179, Encyclopedia Britannica, Inc. (Chicago, 1986).

The average particle size of the components used is preferably about 0.1 to 10 microns.

The mixture is prepared by any other convenient mixing method which does not aggregate the components or vice versa. Such mixing can be integrated with the grinding operation (if present) of the components as required.

The degree of polishing can be measured by the manufacturer's recommended method using an Einlehner AT polishing tester, and such apparatus and methods are known in the art.

In another example, the present invention relates to an antiblocking agent made from a mixture of talc and a component selected from the group consisting of feldspar, lower stone and lower stone islands, wherein the ratio of talc to a component selected from the group consisting of feldspar, lower stone and lower stone islands Provides significantly greater antiblocking action than each component.

In a preferred embodiment, the ratio of the two components is about 1/3 to 3/1 (about 25% to 75% is talc and the rest is a component selected from the group consisting of feldspar, lower and lower selenary cancer), more preferred Preferably about 45/55 to 75/25.

The antiblocking action preferably produces blocking of up to about 85% of a single component, preferably up to about 75% of a single component, more preferably up to about 50% of a single component.

Antiblocking agents can be used in the production of polyolefin films, and when so used, preferably the mixture does not significantly degrade optical properties such as haze and transparency.

In another embodiment of the present invention, the present invention relates to a mixture of talc and a component selected from the group consisting of feldspar, lower stone and lower stone islands, wherein the ratio of talc to a component selected from the group consisting of feldspar, lower stone and lower stone islands It provides significantly lower polishing than would be expected from the law, and provides significantly greater blocking protection than each component.

Preferably, the ratio of the talc to the component selected from the group consisting of feldspar, lower and sedimentary islet rock is about 1/3 to 3/1, and the degree of grinding in the mixture is about 50% or less of that predicted from the mixing law, and blocking The inhibitor produces up to about 50% blocking.

The mixture may be formulated in the same reactor as part of the polyolefin resin composition or polyolefin film production, or prepared as a precursor mixture added to the polyolefin resin composition. The order of addition of each component is not critical. When formulated in the same reactor, the components can be added separately in sequence or simultaneously or in separate main batches which are then blended together.

The present invention also relates to a group of talc and feldspar, stone and sedimentary sedimentary rocks, which provides a significantly lower polishing rate than that foreseen from the mixing law for components selected from the group consisting of feldspar, lower and sedimentary selenite. A polyolefin resin composition comprising a mixture of selected components.

In addition, the present invention provides a significantly lower polishing degree than that foreseen from the mixing law, and provides a significantly higher antiblocking action than each component, for a component selected from the group consisting of feldspar, lower stone and lower stone island rocks. The present invention relates to a polyolefin film composed of a polyolefin resin composition comprising talc and a mixture of components selected from the group consisting of feldspar, lower stone and lower stone island rock.

Preferably, the polyolefin resin composition has a ratio of talc to about 1/3 to 3/1 to a component selected from the group consisting of feldspar, lower stone and lower stone island rocks, and about 85% or less of the abrasiveness in the mixture predicted from the mixing law. And a mixture of talc and a component selected from the group consisting of feldspar, lower and lower island ileus, which produces up to about 50% blocking in the composition.

In addition, the present invention is characterized in that the ratio of talc to constituents selected from the group consisting of feldspar, sediment and sedimentary islet rock provides a significantly lower polishing rate than would be expected from the mixing law, talc, feldspar, A polyolefin film comprising a component selected from the group consisting of nepheline and nepheline syenite.

Preferably, the polyolefin film comprising talc and a component selected from the group consisting of feldspar, nepheline and nepheline syenite is selected for a component selected from the group consisting of feldspar, lower stone and lower stone. Talc ratio provides a significantly lower polishing degree than predicted from the mixing law, and the talc ratio to a component selected from the group consisting of feldspar, sediment and sedimentary islet rock provides a significantly greater antiblocking action than each component. do.

The invention is illustrated in more detail by the following illustrative examples which are not intended to limit the scope of the invention.

Example 1

The measurement of the degree of polishing of the antiblocking agent was carried out using an Einlehner polishing tester. Abrasion of minerals and combinations thereof was tested using diatomaceous earth as a control. Talc A (PolyTalc AG609), Talc B (polybloc), Slate Islet Rock (Minex 7), and Diatomaceous Earth (Super Floss) samples were tested. Samples and mix ratios are as follows:

Test 1 = 50/50 * mixture of talc A and lower sebaceous

Trial 2 = 50/50 mixture of talcum B and lower sebaceous

Trial 3 = 75/25 mixture of talc A and lower sebaceous

Trial 4 = 25/75 mixture of talc A and lower sebaceous

Test 5 = 100% Talc A

Trial 6 = 100% Lower Sile

Test 7 = 100% Diatomite

* 50/50 means 50% by weight to 50% by weight.

All samples were tested with Einlehner Model AT-1000 as 10% dry mineral solid slurry. The wear body was a bronze wire screen. The test time was 100 minutes and / or 174000 polishing times. The test results showed the weight loss of the wire in milligrams. The results are posted in Table 1.

TABLE 1

Example 2

In this experiment, diatomaceous earth was used as a control, and talc and sedimentary islet rock alone and in combination was mixed with low density polyethylene resin at 50% of the total load using a Ryestreets twin gear extruder to create an antiblocking main batch. The ratio of talc to lower stone ciliary cancer is 0/100 to 100/0. The main batch was mixed with LDPE and erucamide leveler batches and molded into a 1 mm thick film using a single gear blown film line, containing 2000 ppm total mineral antiblocking agent and 750 ppm erucamide leveling agent. The final film was prepared. The degree of blocking and the optical properties (blur and clarity) of the film product were tested in the following order.

Examination Process:

(1) blocking degree

The degree of blocking was measured using the ASTM D3354-74 method. An 8 "x 8" sample was cut from the lay flat tubing. The double film layer was separated, slowly passed over the embedded bar to remove the static charge, and then joined again to bring the original inner faces into contact with each other. All films were placed under peak load of 1.0 psi for 24 hours using a purified air circulation oven set at 40 ° C. The force required to separate these two layers was measured and expressed in grams.

(2) blur degree

This test was performed according to ASTM D1003. The transmittance of scattered light as it passes through the film specimen. The lower the cloudiness, the better the optical properties of the light transmitting film.

(3) transparency

Measurements were made according to the instrument manual using a Zebedee CL-100 transparency meter. Optical transparency is defined as the clarity in which an object is seen through the film. The higher the transparency, the better the object of the film.

Specific antiblocking minerals were used for these samples. Talc A (PolyTalc AG609), Talc B (polybloc), Lower Stellite (Minex 7), and Diatomaceous Earth (Super Floss). Example 2 The blocking degree, haze and clarity of the samples are reported in Table 2.

TABLE 2

Formulation: 2000ppm antiblocking agent and 750ppm slip in LDPE film

Example 3

In this experiment, the antiblocking main batch of Example 2 was mixed with LDPE and molded into a 1 mm thick film using a single gear blown film line to produce a final film containing 5500 ppm total mineral antiblocking agent. The degree of blocking and the optical properties (blur and clarity) of the film product were tested according to the method described in Example 2. The blocking degree, haze and clarity of the samples are reported in Table 3.

TABLE 3

Formulation: 5500ppm blocking agent for LDPE film (no slim)

Talc C¹ is ABT 2500 talc

An advantage of the present invention is that the mixtures and polyolefin resin compositions of the present invention can be used to produce films with good antiblocking and optical properties (blur and transparency). The precursor mixtures also have low polishing. The combined mixtures exhibit significantly higher synergies than would be expected when antiblocking activity alone was, while maintaining the optical properties and low polishing.

Claims (7)

Talc is a mixture of talc and a component selected from the group consisting of feldspar, nepheline and nepheline syenite, with a ratio of talc to a component selected from the group consisting of feldspar, stone and sedimentary A mixture that provides a polishing degree of 1: 3 and up to about 80% of that predicted from the mixing law. The mixture of claim 1 wherein the ratio is from 45:55 to 1: 3. Antiblocking agent consisting of a mixture of talc and a component selected from the group consisting of feldspar nepheline and nepheline syenite, wherein the ratio of talc to a component selected from the group consisting of feldspar, seine and sedimentary islet cancer. An antiblocking agent that provides an antiblocking action that is 3: 1 to 1: 3 and each produces a degree of blocking of less than about 85% of a single component. 4. The antiblocking agent of claim 3, wherein the mixture does not degrade optical properties when used in a polyolefin film. Talc and components selected from the group consisting of feldspar, nepheline and nepheline syenite as claimed in any one of claims 1, 2, 3 and 4. Polyolefin resin composition comprising a mixture of. 6. The polyolefin resin composition according to claim 5, wherein the degree of polishing in the mixture is about 80% or less of what is expected by the mixing law and produces a blocking degree of about 50% or less. A polyolefin film composed of the polyolefin resin composition of claim 6.