KR960007310B1 - Heat-adhesive polyolefin resin composition - Google Patents

Abstract

The resin is composed of 0.001-5 wt% the mixture of unsaturated ethylene carbonic acid, anhydride or ester monomer and high dense polyethylene, 1-20 wt% a grafted high dense polyethylene mixture, 60-98.9 wt% polyolefine and 0.1-20 wt% adhesive assistant. The unsaturated ethylene carbonic acid is ethacrylic acid, methacrylic acid, acrylic acid, maleic acid, fumaric acid or ithaonic acid; the unsaturated ethylene carbonic acid anhydride is maleicanhydride, dodecinyl succinic anhydride 5-nobonen-2,3-anhydride or nadicanhydride; and the unsaturated ethylene carbonic acid ester is glycidyl metacrylare, 2-hydroxyethyl acrylate, 2-hydroxyethyl metacrylate, monoethyl maliate, diethyl maliate or di-normal-buthyl maliate.

Description

Heat Adhesive Polyolefin Resin Composition

The present invention relates to a heat-adhesive polyolefin resin composition, and more particularly, to high-density polyethylene (HOPE) in which ethylenically unsaturated carboxylic acid, anhydride and ester derivatives are grafted alone or two or more, Non-low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE) or polypropylene (PP) and a heat-adhesive polyolefin resin composition composed of an adhesive agent.

Polyolefin resins are used for various purposes because of their light weight and low price, as well as excellent physical properties.Because of their non-polar properties, polyolefin resins are not compatible with polar materials such as nylon, polyester, aluminum, iron, paper, wood, etc. Its use has been limited. In order to compensate for this problem, a number of patents relating to the composition and method of preparing polyolefins for improving adhesion by chemically grafting polar groups on the polyolefin backbone have been published, but there are still many improvements.

U.S. Patent No. 4,612,155 describes the type and content of bicomponents based on rheological properties with respect to a method of continuously grafting maleic anhydride in the presence of bicomponent.

U.S. Patent No. 4,612,155 describes the type and content of bicomponents based on rheological properties with respect to a method of continuously grafting maleic anhydride in the presence of bicomponent.

U.S. Patent No. 4,762,890 discloses a method of dissolving maleic anhydride and an initiator in a solvent and injecting it into a twin screw extruder with a liquid injector for grafting.

U.S. Patent No. 4,031,062 discloses a composition for enhancing adhesion by adding magnesium oxide to a polypropylene polymer grafted with maleic anhydride.

Korean Patent Publication No. 89-10078 discloses a composition prepared by adding ethylene vinyl acetate copolymer and polybutene.

However, the method of producing an adhesive resin according to the patent has a process improvement or process development for producing an adhesive resin having a more excellent adhesive force because the process is complicated or expensive to manufacture and there is a limit of adhesive performance.

In the present invention, not only the process was simplified but also the adhesive agent and the second component were used to improve the above problems, thereby improving the adhesive performance and improving transparency, processability, impact strength, adhesion to the adherend, and the like.

Therefore, the present invention solves the problems described above, and the polar polymer such as a non-polar substrate such as polyolefin and nilo, polyester, ethylene vinyl alcohol copolymer or the like, such as aluminum, iron, paper, wood, glass, etc. It is an object of the present invention to provide a heat-adhesive polyolefin resin composition having improved adhesion to a substrate and improved adhesion to a polar material.

In order to achieve the above object, the present invention provides a high density polyethylene copolymer in which ethylenically unsaturated carboxylic acid, anhydride and / or ester monomers are grafted at 0.001 to 5% by weight based on the high density polyetherine copolymer. It provides a heat-adhesive polyolefin resin composition composed of-20% by weight, 60 to 98.9% by weight of polyolefin and 0.1 to 20% by weight of tackifier.

Hereinafter, the present invention will be described in detail.

In the present invention, low density polyethylene, linear low density polyethylene, high density polyethylene, homopolypropylene, random polypropylene, block by reaction extrusion method of one or two or more ethylenically unsaturated carboxylic acid, anhydro or ester monomer in the presence of organic peroxide Graft copolymer grafted to one or more polymers of polypropylene, ethylene-propylene-diene copolymer, and one or more selected from the group consisting of low density polyethylene, linear low density polyethylene, high density polyethylene, and polypropylene Melt training is carried out at a predetermined ratio with the imparting agent to prepare a thermal junction crosslinked polyolefin resin composition.

The heat-adhesive polyolefin resin composition of the present invention is a polyolefin resin, nylon or polyester by heat fusion by a method such as co-extrusion, extrusion coating, circular die coating, T-die coating, powder coating, or compression. , Polar polymers such as ethylene vinyl alcohol copolymers and the like and excellent adhesion to polar or non-polar substrates such as aluminum, iron, paper, wood, glass, etc. can be used as a coating or bonding material thereof.

Typical structures include polyamide / thermal adhesive polyolefin resin / polypropylene, polyamide / thermal adhesive polyolefin resin / polyethylene, polyester / thermal adhesive polyolefin resin / polyethylene, metal / heat adhesive polyolefin resin / polyethylene, epoxy Resin / Heat adhesive polyolefin resin / polyethylene, aluminum / heat adhesive polyolefin resin / polyethylene / heat adhesive polyolefin resin / aluminum, polyethylene / heat adhesive polyolefin resin / aluminum / heat adhesive polyolefin resin / polyethylene, crosslinked polyethylene / Heat Adhesive Polyolefin Resin / Aluminum / Heat Adhesive Polyolefin Resin / Crosslinked Polyethylene, Polypropylene / Heat Adhesive Polyolefin Resin / Polyester, Paper / Heat Adhesive Polyethylene, Polyethylene / Heat Adhesive Polyolefin Resin / Glass, Aluminum / Heat Adhesive Polyolefin Resin / Metal, Ethylene Vinyl Alcohol Copolymer / Heat Adhesive Polyolefin resins / polypropylene resins.

The heat-adhesive polyolefin resin composition of the present invention comprises (1) 1 to 20 weight of high density polyethylene having 0.001 to 5% by weight of ethylene unsaturated carboxylic acid, anhydride or ester which is one or two or more grafting monomers. % (2) Low density polyethylene with a density range of 0.89 to 0.93 g / cm ³ , linear low density polyethylene, high density polyethylene or polypropylene with a density of 0.93 to 0.93 g / cm ³ 60 to 98.9 weight ~ (3) Adhesion It consists of 0.1-20 weight%.

Examples of the carboxylic acid among the grafting monomers used in the present invention include etacrylic acid, methacrylic acid, acrylic acid, maleic acid, fumaric acid, itaconic acid, and the like. Examples of yellow include glycidyl methacrylate, 2-hydroxy ethyl acrylate, 2-hydroxy ethyl methacrylate, morning ethyl maleate, diethyl maleate, di-normal-butyl maleate, and the like. Examples of anhydrides include polar compounds having similar chemical structures such as maleic anhydride, dodecynyl succinic anhydride, 5-norbornene-2,3-anhydride, and nadic anhydride. have.

In order to graf the grafting monomer, the graft reaction initiator may be used in the present invention, and such graft reaction initiator may be acyl peroxide, dialkyl or aralkyl-peroxide, peroxyester, hydroperoxide, ketone. One or two or more of those belonging to the group of peroxides, azo compounds and the like may be selected. Examples of the acyl peroxides include benzoyl peroxides, and the like, and examples of dialkyl or aralkyl-peroxides include di-t. -Butyl peroxide, dicumyl peroxide, cumyl butyl peroxide, 1,1-di-t-butylperoxy-3,5,5-trimethyl cyclohexane, 2,5-dimethyl-2,5-dit- Butyl peroxyhexane, bis (t-butylperoxy isopropyl) benzene, and the like, and examples of the peroxy esters are t-butyl perbenzoate, 2,5-dimethyl hexyl-hydro peroxide, P-methane hydro Peroxa Deutane, evacuation hydro peroxide, cumene hydro peroxide, and the like, and ketone peroxide and cyclohexadecane include peroxide, methyl ethyl ketone peroxide, and the like, and examples of azo compounds are azobis isobutyro. Nitrile, and the like.

The grafting monomer is preferably added in an amount of 0.001 to 5.0% by weight, more preferably 0.1 to 2.5% by weight, based on the total base resin, and the initiator is added in an amount of 0.001 to 1.0% by weight, more preferably 0.005 to 0.5% by weight based on the entire base resin. It is desirable to be. In the present invention, other small amounts of additives such as stabilizers and lubricants may be used.

When the content of the grafting monomer is less than 0.001% by weight, it is difficult to impart adhesive performance. When the content of the grafting monomer is higher than 5.0% by weight, various problems such as poor reaction efficiency, discoloration, and excess unreacted monomer remain. Is generated.

In addition, when the amount of the initiator is less than 0.001% by weight, the grafting reaction of the graft monomer is difficult to occur, and when the amount of the initiator is more than 1.0% by weight, the crosslinking reaction of the base resin is severely accompanied with the grafting reaction, resulting in poor flowability. Problems arise.

In addition, when the amount of the initiator is less than 0.001% by weight, the grafting reaction of the grafting monomer is difficult to occur, and when the amount of the initiator is more than 1.0% by weight, the crosslinking reaction of the base resin occurs severely with the grafting reaction, resulting in poor flowability. Problems arise.

The grafted high density polyethylene has a density of 0.93-0.97 g / cm ³ and a melt index of 0.1-5.5 g / 10 min. In the composition of the present invention, the grafted high-density polyethylene is preferably 1 to 20% by weight, and when less than 1% by weight, the adhesive force with the adherend is hardly shown, and the residual amount of the unreacted monomer is increased so that the adhesive force is rapidly decreased. There is a problem.

The ungrafted unmodified low density polyethylene of the present invention has a melt index of 0.1 g / 10 minutes to 50 g / 10 minutes, and the unmodified linear low density polyethylene has a melt index of 0.1 g / 10 minutes to 60 g / 10 minutes, and alkene co It is preferable to use what has 4-10 carbon atoms and contains 1-15 weight% of alkene comonomer of a monomer.

In the present invention, the ungrafted unmodified high density polyethylene having a melt index (MFR) of 0.1 to 55 g / 10 minutes, homopolypropylene having a melt index of 0.1 to 40 g / 10 minutes, and a melt index of 0.1 to 80 g / 10 minutes and an ethylene content of 0.5 to Preference is given to using ungrafted polypropylenes selected from 30% by weight block copolymers or random copolymers having a melt index of 0.1 to 80 g / 10 minutes and an ethylene content of 0.2 to 10% by weight.

In this case, when two or more selected from the group consisting of ungrafted unmodified low density polyethylene, linear low density polyethylene, high density polyethylene, and polypropylene, each polyolefin content should be 1% by weight or more. If the content is less than 1% by weight, the effect of improving transparency and efficiency obtained by using the combination will not appear.

As the adhesive agent, natural resin adhesives such as rosin, rosin ester, hydrogenated rosin ester, terpene, aliphatic (C5) petroleum resin, acid-modified aliphatic petroleum resin, alicyclic petroleum resin, hydrogenated alicyclic petroleum Resin, aromatic (C8, C9) petroleum resin, hydrogenated aromatic petroleum resin, aliphatic (C5) aromatic (C8, C9) copolymerized petroleum resin, styrene petroleum resin, alkyl phenol petroleum resin, coumarone ind coal tar, etc. Synthetic resin tackifiers.

The graft polymer of the present invention is a high-density polyethylene by coating a constant content of one or two or more of the graft monomers and a predetermined amount of the initiator in a supermixer to produce a graft polymer by continuously reacting extrusion in a twin screw extruder, At this time, the residence time should be maintained long enough for the grafting reaction to occur. Unreacted grafting monomer is removed by vacuum at the end of the extruder.

The present invention by mixing the graft polymer prepared as described above, low density polyethylene, linear low density polyethylene, high density polyethylene or polypropylene with a tackifier in a tumble mixer and melt kneading at a temperature of 180 ~ 240 ℃ in a single screw extruder According to the present invention, a heat-adhesive polyolefin resin composition can be prepared.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to the following examples, and various changes can be made by those skilled in the art without departing from the scope and spirit of the present invention.

Example 1

Supermixer 2.0% by weight maleic hydride and 0.1% by weight of bis (t-butyl peroxy isopropyl) benzene based on high density polyethylene (density 0.96g / m ³ , melt index 20g / 10min, Yugong, Korea) (Ox., Ltd., Korea) and rotated at 200 rpm for 2 minutes to evenly coat the surface of the high-density polyethylene, then twin-screw extruder (400 Continuous reaction extrusion using W & P Germany) produced a high density polyethylene (melt index 4.0 g / 10 min) copolymer with maleic anhydride grafted at least 0.5% by weight.

10% by weight of the polymer and the low-density polyethylene (density 0.90g / cm ³ melt index 2.5g / min) and the adhesive imparting agent (songjin ester, softening point 90 ± 5, acid value 40-50) tumble in the ratio of Table 1 Mixing (Hanil Rationalization Machine, Korea) single screw extruder (65 Shinhwa Industrial Co., Ltd.), melt kneading at 180 ~ 240 ℃ to prepare a heat-adhesive polyolefin resin composition. After preparing the adhesive force measurement specimen as described below was measured for adhesion, the results are shown in Table 1.

[Adhesive force measurement specimen preparation]

A 70 μm film was prepared from the heat-adhesive polyolefin resin composition, placed on a sheet of linear low density polyethylene (density 0.919 g / cm ³ , melt index 1.0 g / 10 min) having a thickness of 2 mm, and then the adherend was placed at 190 ° C. and 4 kg. After thermal bonding for 2 minutes at a pressure of / cm ^2, the phase was cooled for 2 minutes at a pressure of 1kg / cm ² and cut into a width of 2.5cm and a length of 20cm.

[Adhesion Measurement]

T-pen adhesion was measured in the tensile tester (INSTRON 6025) by the method of ASTM D1876-72, the average adhesion value between 50 ~ 250mm was obtained in kg / cm.

TABLE 1

EXAMPLES 2-7

20% by weight of the graft polymer and linear low density polyethylene (density 0.92kg / cm ² , melt index 1.0g / 10min) by changing the weight ratio of the graft monomer as shown in Table 2 in the same manner as in Example 1 % And petroleum resin (songjin ester type, softening point 90 ± 5, acid value 40-50) by melt kneading to prepare an adhesive specimen by the method of Example 1 to measure the adhesive strength, as shown in Table 2.

TABLE 2

[Examples 8-17]

The unmodified linear low density polyethylene (density 0.920 g / cm ³ , while changing the content of the graft copolymer grafted with 0.5% by weight of the polar monomer in the graft high density polyethylene prepared by the method of Example 1 to 1-20% by weight) Adhesion to the aluminum of the heat-adhesive polyolefin resin composition prepared by melt kneading the melt index of 2.5g / 10 minutes) and 5% by weight of petroleum resin (songjin ester, softening point 90 ± 5, acid value 40-50) was measured, The results were shown in Table 3.

TABLE 3

[Examples 28-21]

20% by weight of the graft copolymer in which 0.5% by weight of the polar monomer is grafted in the graft high density polyethylene prepared by the method of Example 1, and unmodified low density polyethylene (density 0.91 g / cm ³ , melt index 3g / 10 minutes) , Linear low density polyethylene (density 0.92 g / cm ³ , melt index 0.5 g / 10 min). Or 75% by weight of polypropylene (melt index 2.2g / 10min) and 5% by weight of petroleum resin (songsin ester, softening point 90 ± 5 acid value, 40-50) by melt kneading to the aluminum of the heat-adhesive polyolefin resin composition Adhesion was measured, and the results are shown in Table 4.

TABLE 4

As can be seen from the above table, the adhesive polyolefin resin composition of the present invention exhibits much better synergistic effect compared to the heat-adhesive polyolefin resin composition prepared by melt kneading a polymer and a polyolefin resin grafted with the same polar group. It has adhesive strength, and it can be seen that physical properties such as transparency and impact strength are also improved.

Claims (10)

1-20% by weight, 60-98.9% polyolefin, and adhesion of ethylenically unsaturated carboxylic acid, anhydride and / or ester monomer, from 0.001 to 5% by weight, based on high density polyethylene copolymer Heat-adhesive polyolefin resin composition comprising 0.1 to 20% imparting agent. 2. The ethylenically unsaturated carboxylic acid anhydride of claim 1, wherein the ethylenically unsaturated carboxylic acid is ethacrylic acid, methacrylic acid, acrylic acid, maleic acid, fumaric acid, or itaconic acid. Is maleic anhydride, dodecynyl succinic anhydride 5-norbornene-2,3-anhydride, or nadic anhydride, wherein the ethylenically unsaturated carboxylic ester is glycidyl methacrylate, A heat-adhesive polyolefin resin composition, characterized in that 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, monoethyl maleate, diethyl maleate, or di-normal-butyl maleate. The heat-adhesive polyolefin resin composition according to claim 1, wherein the high density polyethylene has a density of 0.93-0.97 g / cm ³ and a melt index of 0.1-5.5 g / 10 minutes. The heat-adhesive polyolefin resin composition according to claim 1, wherein the polyolefin is one or more selected from the group consisting of ungrafted unmodified low density polyethylene, linear low density polyethylene, high density polyethylene, and polypropylene. The heat-adhesive polyolefin resin composition according to claim 4, wherein the ungrafted unmodified low density polyethylene has a density of 0.89 to 0.9 g / cm ³ and a melt index of 0.1 g / 10 minutes to 50 g / 10 minutes. The method of claim 4, wherein the ungrafted unmodified linear low density polyethylene has a density of 0.89-0.93 g / cm ³ , a melt index of 0.1 g / 10 minutes to 60 g / 10 minutes, an alkel comonomer having 4 to 10 carbon atoms, A heat-adhesive polyolefin resin composition, characterized in that the content of alkene comonomer is 1 to 15% by weight. The heat-adhesive polyolefin resin composition according to claim 4, wherein the ungrafted unmodified high density polyethylene has a density of 0.93-0.97 g / 10 minutes and a melt index (MFR) of 0.1-55 g / 10 minutes. The non-grafted polypropylene homopolypropylene having a melt index of 0.1 to 40 g / 10 minutes, a block copolymer having a melt index of 0.1 to 80 g / 10 minutes and an ethylene content of 0.5 to 30 wt%, or a melt index of 0.1 to 5 Heat-adhesive polyolefin resin composition, characterized in that the random copolymer of 80g / 10min and 0.2 to 10% by weight of ethylene. 5. The method of claim 4, wherein two or more selected from the group consisting of the ungrafted unmodified low density polyethylene, the linear low density polyethylene, the high density polyethylene, and the polypropylene are combined and one is mainly used, and the other is 1 wt% or more. A heat adhesive polyolefin resin composition. The method of claim 1, wherein the adhesive agent is rosin, rosin ester, notebook rosin ester, terpene, aliphatic (C5) petroleum resin, acid-modified aliphatic petroleum resin, alicyclic petroleum resin, diary alicyclic petroleum resin, aromatic Group consisting of (C8, C9) copolymer petroleum resin, notebook aromatic petroleum resin, aliphatic (C5) aromatic (C8, C9) copolymer petroleum resin, styrene petroleum resin, alkylphenol petroleum resin, and coumarone indene coal tar Heat-adhesive polyolefin resin composition, characterized in that one or more selected from.