KR830001396B1 - Resin Composition - Google Patents

Abstract

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Description

Resin Composition

The present invention relates to a novel resin composition having good moldability and excellent soft resin properties and having good heat adhesiveness.

In general, in the field of packaging materials, the requirements vary, so that various materials having different physical properties are preferable.

For example, polyvinyl chloride has the upper hand in the field of soft materials. However, it is preferable to convert to polyolefin resin because the generation of corrosive gas or stability of residual monomer or plasticizer becomes a problem when incineration of waste. .

Therefore, in order to soften a polyolefin resin, synthetic rubber and a low molecular weight softening agent should be mix | blended, but surface adhesiveness, oil resistance, and heat resistance generally fell.

On the other hand, as composite materialization progresses, adhesion of polyolefin or a material having excellent properties of polyolefin to other kinds of materials is required.

For example, various materials and polyolefins are compounded by using a carboxyl group-containing polyolefin as an adhesive resin by coextrusion molding, extrusion lamination, extrusion coating, powder coating, or the like.

Therefore, in this case, the target material which can be compounded with a carboxyl group-containing polyolefin is limited. For example, compounding of vinyl chloride resin, acrylic resin, styrene resin, high nitrile resin, polyester resin, etc. is difficult. , Metals, polyamide resins, ethylene-vinyl ester copolymer saponification and the like also insufficient.

The inventors of the present invention have found a resin composition that can solve the above problems at once while completing a study on polymer-alloy, thereby completing the present invention.

That is, the present invention contains 5-70 parts by weight of thermoplastic polyurethane elastomer and at least one functional group selected from the group consisting of carboxylic acid groups, carbonate groups, carboxylic acid anhydride groups, amide groups, hydroxyl groups, and epoxy groups in the main chain or side chain. The present invention relates to a resin composition comprising 95-30 parts by weight of a copolymer mainly composed of a modified polyolefin or an olefin containing a functional group.

Thermoplastic polyurethane elastomers used in the present invention are polyoxytetramethylene glycol, polyetherdiols such as polyethylene ether glycol, polyethylene adipate, poly (1,4-butylene adipate), poly (1, Bifunctional polyol components such as 6-hexane adipate), polytetramethyl sebacate, polycaprolactone, polyhexamethylene carbonate or mixtures thereof, ethylene glycol, 1,4-butylene glycol Glycols, glycols such as 1,6-hexamethylene glycol, bishydroxyethoxybenzene, ethylenediamine, 1,4-butylenediamine, diamines such as cyclohexanediamine, trigendiamine, hydrazine, mono Bifunctional low hydrazines such as alkylhydrazines, hydrazines such as N, N'-diaminopiperazines, dihydrazides such as carbodihydrazides, dihydric acid dihydrazides, water or mixtures thereof Molecular weight compound component, diphenylmethane diisocyanate, dicyclohexyl methane diisocyanate, isocyanate, isoborone diisocyanate, triene diisocyanate, xylene diisocyanate, isopropylidenebis (4-phenylisocyanate), tetramethylene diisocyanate, hexa Diisocyanate components such as methylene diisocyanate or mixtures thereof.

The thermoplastic polyurethane elastomer has a molar ratio [NCO] / [AH] ≒ of the active hydrogen group [AH] contained in the bifunctional polyol component and the functional low molecular weight compound component and the [NCO] group contained in the diisocyanate component. It is a linear polymer reacted with 1.

1, 바람직하게는 일반적으로 0.95<[NCO]/[AH]

1로 합성한 완전 열가타입과 일반적으로 1<[NCO]/[AH]<1.1로 합성한 불완전 열가소성 타입의 양자를 사용할 수 있다.In the present invention, generally 0.5 <[NCO] / [AH]

1, preferably generally 0.95 <[NCO] / [AH]

Both full thermoplastics synthesized at 1 and incomplete thermoplastics synthesized at 1 <[NCO] / [AH] <1.1 can be used.

The former takes a linear structure at the terminal of a hydroxyl group or an amino group, and the latter takes a linear structure having a crosslinking point in part.

Such thermoplastic polyurethane elastomers can be produced by various known methods by the bulk polymerization method or the solution polymerization method.

In the present invention, the copolymer mainly composed of modified polyolefin or olefin contains at least one functional group selected from the group consisting of carboxylic acid group, carbonate group, carboxylic acid anhydride group, amide group, hydroxyl group and epoxy group in the main chain or side chain thereof. For example, each of the following types is possible.

One of them is a modified polyolefin obtained by crosslinking (grafting) an unsaturated carboxylic acid or a derivative thereof and another functional vinyl monomer to a polyolefin.

In this case, as the polyolefin, polyolefin such as high density polyethylene, medium density polyethylene, low density polyethylene, polypropylene, polybutene, poly 4-methylpentene-1, copolymer of ethylene and α-olefin, copolymer of propylene and α-olefin, etc. , Ethylene-propylene rubber, ethylene-propylene-diene tertiary rubber, butyl rubber, butadiene rubber, low crystalline ethylene-propylene copolymer or low crystalline ethylene-butene copolymer, or low crystalline propylene-butene copolymer Polyolefin-based elastomers such as polyolefin-based thermoplastic elastomers, polyolefin-based thermoplastic elastomers mainly composed of blends of polypropylene and ethylene-propylene, And mutual blend mixtures of various polyolefins.

Meanwhile, in the present invention, unsaturated carbonic acid or derivatives thereof, and other functional vinyl mononers are exemplified by acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, sorbic acid, sorbic acid, carboxylic acid, maleic anhydride, anhydride, and the like. Anhydrides such as itaconic acid, amides such as acrylic acid amide and methacrylic acid amide, epoxys such as acrylic acid glycidyl and methacrylic acid glycidyl, acrylate 2-hydroxyethyl, 2-hydroxyethyl methacrylic acid and polyethylene glycol Hydroxy compounds, such as chol monoacrylate, Metal salts, such as sodium acrylate, sodium methacrylate, and zinc acrylate, can be frozen, and mixed use with each other is also possible.

Especially, acrylic acid, maleic acid, and maleic anhydride obtained the preferable result.

In addition, when the above monomers are used, co-graft copolymerization may be performed simultaneously with other types of monomers such as styrene, vinyl acetate, acryl ester, and methacrylic ester.

The amount of unsaturated carbonic acid or derivatives thereof and other functional vinyl monomers contained in the graft-modified polyolefin is preferably 0.005-5 mol%, more preferably 0.01-0.1 mol%.

The amount can be exerted even if the functional group contained in the polyolefin has a strong interaction with the thermoplastic polyurethane elastomer.

However, if it is less than the above range, a remarkable effect cannot be obtained as in the present invention, and if more than the above range, the moldability and thermal stability of the composition are lowered, which is undesirable.

In addition, various methods can be employed to form a polyolefin graft-modified with an unsaturated carbonic acid or a derivative thereof or another functional vinyl monomer.

One method is to melt homogenize by mixing polyolefin, unsaturated carbonic acid or derivatives thereof, other functional vinyl monomer and radical generator at the same time, and the other is unsaturated carbon acid or polycarboxylic acid dissolved or suspended in a suitable solvent. And derivatives thereof, other functional vinyl monomers and radical generating agents.

On the other hand, it is also possible to cause the above reaction in the presence of the thermoplastic polyurethane elastomer according to the present invention.

Another modified polyolefin according to the present invention is a modified product obtained by grafting an unsaturated carbonic acid or a derivative thereof and another functional vinyl monomer onto a saponified product of an ethylene-vinyl ester copolymer or a saponified product of an ethylene-vinyl ester copolymer. This is possible.

In this case, the ethylene-vinyl ester copolymer is preferably a copolymer mainly composed of ethylene, and the ethylene content is preferably 50 mol% or more. The saponification degree is preferably in the range of 10-100%.

Those in this range form a composition having good moldability and physical properties with the thermoplastic polyurethane elastomer.

On the other hand, modified products grafted with the above unsaturated carboxylic acid, derivatives thereof, and other functional vinyl monomers in the saponified product of the above ethylene-vinyl ester copolymer can also be used in the present invention.

Distillation, amount, and modification method of the monomer is the same as the modified polyolefin.

Copolymers mainly composed of olefins that can be used in the present invention can be copolymers of α-olefins with unsaturated carboxylic acids or derivatives thereof and other functional vinyl monomers, and partial metal salts of copolymers of -olefins and unsaturated carboxylic acids. Ionomer resins are also possible.

Examples of ionomer resins and partial ethylene resins of ethylene-acrylic acid copolymers, ethylene-methacrylic acid copolymers, ethylene-acrylic acid-methacrylic acid ester copolymers, and ethylene-acrylic acid-methacrylic acid ester copolymers Eye owner resins made of partial metal salts;

As mentioned above, the copolymer mainly having various modified polyolefin and olefin can also be mixed and used.

The mixing ratio of the above thermoplastic polyurethane elastomer and the copolymer mainly composed of the above modified polyolefin or olefin is required to be in the range of 5-70 parts by weight of the former and 95-30 parts by weight of the latter.

In particular, when the resin composition of the present invention is used as an excellent soft resin, the compounding ratio may be selected within the above range according to the purpose of use, preferably the former is in the range of 10-50 parts by weight and the latter is in the range of 90-50 parts by weight. It is desirable to have good moldability and excellent soft resin properties.

On the other hand, when the resin composition of the present invention is used as the adhesive resin, the compounding ratio can be selected within the above range depending on the purpose of use, in particular, the reverse phase of the "sea-do" dispersion structure The compounding ratio of (逆轉 相 域) is preferable.

This state can also be said to be the parallel concentration range of the "solution-degree" dispersion state of both.

That is, the thermoplastic polyurethane elastomer in the resin composition is "harmful" (continuous phase) for a material surface having adhesiveness to the thermoplastic polyurethane elastomer but low adhesiveness to a modified polyolefin or a copolymer mainly composed of an olefin. It is preferable to use a modified phase in which the modified polyolefin or the copolymer mainly composed of olefins is "degree" (discontinuous phase).

Conversely, copolymers mainly composed of modified polyolefins or olefins in the resin composition are "harmful" in terms of a material surface having adhesiveness to a copolymer mainly composed of modified polyolefins or olefins but low adhesion to thermoplastic polyurethane elastomers. As the (continuous phase), a dispersed state in which the thermoplastic polyurethane elastomer becomes "degrees" (discontinuous phase) is preferable.

By the way, when different types of materials are simultaneously bonded with the resin composition of the present invention as described above, the structure in which the positive components in the resin composition are both "sea" (continuous phase) is preferable.

In other words, the dispersion structure of the thermoplastic polyurethane elastomer and the modified polyolefin or the copolymer mainly composed of the olefin in the resin composition of the present invention is reversed in the dispersion state of "sea-degree", and the dispersed state of "sea-degree" is destroyed. Preferred areas are preferred.

As such, the optimum blending ratio is changed depending on the melt viscosity, chemical affinity, manufacturing method, molding method, and the like, in the concentration region of the positive product for the appearance of the dispersed state, and the thermoplastic polyurethane elastomer is 20 to 60 parts by weight, the modified polyolefin or the olefin. In order to obtain optimum adhesiveness, it is preferable from the viewpoint of moldability and economics that the copolymer mainly containing is in the range of 80-40 weight part.

On the other hand, even if the dispersion structure composed of a thermoplastic polyurethane elastomer and a copolymer mainly composed of a modified polyolefin or an olefin has a clear “sea-degree” dispersion structure, the short diameter of the discontinuous particles to be “degrees” When the microdispersion is less than 100 mu, the same effect as in the region where the above-described "phase-degree" phased state is destroyed is obtained.

In particular, the smaller the shorter diameter of the discontinuous phase particles is, the more preferable is 50 µm or less, more preferably 20 µm or less.

When the shorter diameter of the discontinuous phase particles exceeds 100 mu, in particular, the fixing strength due to thermal bonding is lowered, and physical properties, in particular, toughness and moldability as soft resins are also lowered.

The concentration range of the cationic component for the application of such a dispersed state, but the optimum mixing ratio is changed by the melt viscosity, chemical affinity, manufacturing method or molding method of the two can be selected within the above range.

The melt kneading method is the simplest to prepare the resin composition of the present invention.

It can be manufactured by melt-kneading with an apparatus such as a single screw extruder, a multi-screw extruder, a ban bury mixer, a Kneader, a mixing roller, etc. mixed at a predetermined compounding ratio.

It is to be noted that the kneading degree affects the powder phase and physical properties of the resin composition, and that the thermal stability of the thermoplastic polyurethane elastomer is low.

It is preferable to raise the kneading degree sufficiently in the range which does not impair the thermal stability of a thermoplastic polyurethane elastomer.

In addition to the said composition, the resin composition of this invention can add another kind of synthetic elastomers.

In addition, various additives such as stabilizers, ultraviolet absorbers, lubricants, antistatic agents, fillers, fibrous reinforcing agents, flame retardants, tackifiers, dyes, and pigments may be added.

The resin composition of the present invention is applied to various applications by applying general molding processing methods to thermoplastic resins such as compression molding injection molding, various extrusion molding, calendar molding, foam molding, stretching processing, surface processing, etc. The present invention is also used for complexing with various materials to use as an adhesive by extrusion molding, coextrusion sheet, coextrusion coating, etc., various coextrusion molding, laminating processing, extrusion coating, and the like.

Hereinafter, the present invention will be described in detail by way of examples, but is not limited thereto.

In Examples and Reference Examples, parts and percentages indicate parts by weight and weight percent, respectively.

Example 1

The maleic anhydride and the high density polyethylene were melt kneaded in the presence of a radical generator to obtain a maleic anhydride graft modified high density polyethylene having a MI of 0.3, a density of 0.953, and a content of maleic anhydride of 0.1%.

The modified high-density polyethylene and the thermoplastic thermoplastic elastomer (manufactured by Japanese Polyurethane Co., Paraprene P ₂₂ S) of the thermoplastic resin were used as an extruder in the mixing ratio as shown in the first table, and pellets were obtained by melt mixing at 190 ° C. The obtained pellet was press-molded and the tensile characteristic was measured by JISK 6301.

The results are shown in the first table.

Reference Example 1

In the same manner as in Example 1 except that the use of unmodified high density polyethylene having a density of MI 0.3 and a density of 0.953 was used instead of the maleic anhydride graft modified high density polyethylene used in Example 1. The results are shown in the first table.

[Table 1]

Example 2

60 parts of maleic anhydride-modified high-density polyethylene used in Example 1 and 40 parts of various thermoplastic polyurethane elastomers listed in Table 2 were kneaded in the same manner as in Example 1 to prepare various resin compositions and to evaluate physical properties. 2 is shown.

Reference Example 2

Various resin compositions were prepared and evaluated for physical properties in the same manner as in Example 2 except for using the non-flammable high density polyethylene used in Reference Example 1 instead of the maleic anhydride graft modified high density polyethylene used in Example 2.

The results are shown in the second table.

[Table 2]

(1) Sumimodo Bayer Urethane Co., Ltd.

(2) Uni-Royal Corporation

(3) Kasei Abjohn Co., Ltd.

(4) Mobay chemical company

Example 3

The various resin compositions obtained in Example 1 were molded into a film having a thickness of about 100 µm and inserted between a high density polyethylene film having a thickness of about 100 µm and a polyethylene terephthalate biaxially stretched film having a thickness of about 19 µm at a temperature of 200 ° C. and a pressure of 20 kg / cm 2. Press to bond.

Peel strength (T-Piccol, 200 mm / chuck speed) of the adhesive sample was measured.

The results are shown in Table 3.

Reference Example 3

Peeling strength was measured in the same manner as in Example 3 using various resin compositions obtained in Reference Example 1 by performing an adhesion test on a high density polyethylene and a polyethylene terephthalate film.

The results are shown in Table 3.

[Table 3]

(1) Unit: kg / 25mm

(A) Destruction of the adherend

(B) adhesive destruction

(C) interfacial peeling

Reference Example 4

60 parts of maleic anhydride graft modified high density polyethylene used in Example 1 and 40 parts of various thermoplastic elastomers described in Table 4 were kneaded in the same manner as in Example 1 to prepare various resin compositions, and the same as in Example 3 Peel strength was measured by the adhesion test on the terephthalate film.

The results are shown in Table 4.

[Table 4]

(1) Asahi Chemical Co., Ltd. Product Name: Tapuprene AT

방적(주) 상품명 : 페루프렌 P40H(2) Toyo

Product name: Peruprene P40H

(3) Mitsui Petrochemical Industries, Ltd. Product Name: Tarpmer P0680

Example 4

60 parts of copolymers mainly composed of various modified polyolefins or methylene listed in Table 5 instead of the high density polyethylene of maleic anhydride used in Example 1 and 40 parts of thermoplastic polyurethane elastomer used in Example 1 It knead | mixed similarly and manufactured various resin compositions.

This was molded into a film of about 100 mu and inserted between the various materials to be coated below, and thermally bonded at a temperature of 200 ° C. and a pressure of 20 kg / cm 2 to measure the peel strength. The results are shown in Table 5.

Material to be deposited:

HDPE: High density polyethylene film about 100μ thick

LOPE: Low density polyethylene film about 100μ thick

PP: crystalline polypropylene film about 100μ

PET: Polyethylene terephthalate biaxially oriented film about 19μ thick

PA: Nylon 66 unstretched film about 100μ thick

A1: hard aluminum thin plate about 100μ thickness

Iron: soft polished steel plate about 1mm thick

Paper: Single Sconce

[Table 5]

(1) MI 1.0, density 0.945, maleic anhydride content 0.1%

(2) MI 1.3, density 0.920, maleic anhydride content 0.2%

(3) MFI 8, density 0.91, maleic anhydride content 0.1%

(4) MI 3, vinyl acetate content 10%, maleic anhydride content 0.2%

(5) MI 15, vinyl acetate content 30%, saponification degree 60%, maleic anhydride content 0.2%

(6) MFI 20, density 0.91, acrylic acid content 5%

(7) MI 5, density 0.94, methacrylic acid content 10%

(8) Mitsui Polychemical Co., Ltd.

(A) Substrate breakdown (C) Interfacial peeling

(B) breaking adhesive

Reference Example 5

Various modified polyolefins and thermoplastic polyurethane elastomers used in Example 4 were each molded into a film having a thickness of 100 mu alone.

Using this film, the adhesiveness was evaluated after manufacturing the test piece by the various to-be-adhered material of Example 4. The results are shown in Table 6.

[Table 6]

Example 5

The low density polyethylene [II] of maleic anhydride and M12 was melt kneaded in the presence of a radical generator to obtain a modified maleic acid graft modified low density polyethylene [I] having a MI 1.2, a density of 0.919, and a maleic anhydride content of 0.2%. On the other hand, low density polyethylene [IV] of maleic anhydride and M15 was melt kneaded in the presence of a radical generator to obtain a maleic anhydride graft modified density polyethylene [II] having a MI 1.5, a density of 0.918, and a maleic anhydride content of 0.5%. .

These modified low density polyethylene and the thermoplastic polyurethane elastomer used in Example 1 were obtained by carrying out melt-mixing extrusion at 190 degreeC using the extruder at the compounding ratio shown in Table 7. The obtained ferret was formed into a film by the inflation film film forming machine, and the film of 40 micrometers in thickness was obtained.

In order to know the flexibility of these films, the fall impact strength (R = 1.8 cm of the weight, 250 cm of the height of the weight) was measured. In addition, in order to confirm the dispersion structure of the resin composition, the film was dyed with a disperse dye to dye only the polyurethane phase. The dispersion structure is expressed as A / B in which the polyurethane phase is "do" and the polyethylene phase is "sea", and vice versa. In addition, it is represented by AxB that the dispersion structure of "sea-do" is mixed. In addition, there is no indication that the short diameter of "do" is 10 micrometers or less, and the 10 micrometer or more added the X mark.

Reference Example 6

Instead of using modified low density polyethylene in Example 3, except for using the unmodified low density polyethylene, the resin composition was prepared and evaluated in the same manner as in Example 5. In Example 5, the film was formed without any problem at the time of in-flation film formation. In Reference Example 6, however, the haloblocking was carried out between resins and winding rollers, which made it difficult to stabilize the film.

[Table 7]

Since the resin composition of the present invention is a blend of a polyolefin resin and a thermoplastic polyurethane elastomer, it has a soft resin property, which has a defect in surface adhesiveness, excellent oil resistance and heat resistance, and excellent thermal adhesiveness of various materials. This is the material. Since the resin composition of the present invention is used as a polyolefin resin having a functional group having a chemical interaction of the thermoplastic polyurethane elastomer, the compatibility and dispersibility of both components can be good and excellent soft resin properties can be exhibited.

The resin composition of the present invention can be used for use as a heat adhesive between a wide range of materials by arbitrarily selecting the blending ratio, viscosity, and manufacturing method of a modified zoleolefin or an olefin-based copolymer and a thermoplastic polyurethane elastomer.

Claims (1)

Modified polyolefin containing 5-70 parts by weight of thermoplastic polyurethane elastomer and at least one functional group selected from the group consisting of carboxylic acid group, carbonate group, carboxylic acid anhydride group, amide group, hydroxyl group and epoxy group in the main chain or side chain, or A resin composition comprising 95-30 parts by weight of a copolymer mainly composed of olefins containing the above functional groups.