JP3488556B2 - Laminate - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate, and more particularly to a laminate of a synthetic resin useful as a container or packaging material which requires chemical resistance, gas barrier property and liquid barrier property.

[0002]

2. Description of the Related Art Polyolefin is a resin that has excellent mechanical properties, thermal properties, chemical properties, electrical properties, etc., and is an easy-to-process and inexpensive resin, so it is widely industrially produced and used in various fields. There is. However, polyolefin has insufficient gas barrier property and liquid barrier property.
Therefore, in order to improve these properties, a laminate of a polyolefin and a polyalkenyl terephthalate resin such as polyethylene terephthalate having excellent gas barrier properties and liquid barrier properties has been developed. However, since polyolefin is a non-polar resin in terms of chemical structure, it has a drawback that it has poor melt adhesiveness when producing a laminate with the above polyalkenyl terephthalate resin.

Therefore, various methods for imparting adhesiveness have been developed. As a typical method thereof, modification obtained by graft polymerization of an unsaturated compound having an acid anhydride, a carboxyl group, an epoxy group or the like polar group in a polyolefin main chain by a solution method, a suspension method, a melting method or the like. Polyolefins and olefin monomers and acid anhydrides,
A method of using a copolymer of an unsaturated compound having a polar group such as a carboxyl group or an epoxy group as an adhesive material has been proposed and widely applied. According to this method, without impairing the aforementioned properties that the polyolefin originally has,
Adhesiveness with the polyalkenyl terephthalate resin is imparted. However, the above-mentioned conventional adhesive material has a slow adhesive reaction rate with the polyalkenyl terephthalate resin, and thus a high adhesive reaction temperature or a long adhesive reaction time is required to obtain sufficient adhesiveness.

Another known method for modifying a polyolefin is to graft a highly reactive unsaturated compound containing an isocyanate group onto the main chain of the polyolefin (JP-A-1-319507). This method is a method of grafting in a solvent, and a free radical initiator (graft polymerization catalyst) is used in an amount of 0.2 per 100 parts by weight of polyolefin.
It is often used at -40 parts by weight. The modified polyolefin obtained is used as an additive for lubricating oil. The modified polyolefin graft-polymerized with a large amount of free radical initiator is expected to be effective as an additive for lubricating oil, but from the viewpoint of adhesiveness with the polyalkenyl terephthalate resin, polyolefin originally has In addition to the deterioration of the physical properties, the homopolymerized unsaturated compound containing an isocyanate group remains in the modified polyolefin to a considerable extent, which is not preferable as an adhesive.

Further, a copolymer of ethylene and an unsaturated compound containing an isocyanate group (JP-A-2-300217) is known, and it is possible to use this as an adhesive, but the adhesive functional group is the main chain. Since it is present inside, the molecular mobility of the adhesive functional group is limited as compared with the graft type, and there is a drawback that sufficient adhesiveness cannot be obtained at low temperature in a short time.

[0006]

Adhesion between a polyolefin and a polyalkenyl terephthalate resin requires high temperature or a long time in the conventional method using a modified polyolefin or the like as an adhesive layer. An object of the present invention is to provide a laminate having excellent adhesiveness between a polyolefin and a polyalkenyl terephthalate resin by developing a resin that enables this adhesion at a low temperature for a short time.

[0007]

The present invention provides a modified polyolefin obtained by grafting an unsaturated compound containing an isocyanate group onto a polyolefin, and preferably the modified polyolefin grafted under a specific condition has an adhesive property to a polyalkenyl terephthalate resin. Was found to be good and was based on this. That is, the present invention relates to a laminate in which (A) a resin layer made of polyolefin and (B) a polyalkenyl terephthalate resin layer are adhered by a modified polyolefin resin layer obtained by grafting (C) a polyolefin with an isocyanate group-containing unsaturated compound. Is.

In the above invention, the modified polyolefin is a polyolefin containing an isocyanate group-containing unsaturated compound in an amount of 0.001 to 1.5 based on the olefin monomer.
Those grafted by mol% are preferred. Further, as a method for obtaining a modified polyolefin, (a) polyolefin 1
00 parts by weight, (b) 0.01-10 parts by weight of an isocyanate group-containing unsaturated compound, and (c) 0.0 of an organic peroxide.
A mixture of 01 to 0.18 parts by weight is melt-reacted,
The method of grafting the above-mentioned unsaturated compound containing an isocyanate group to polyolefin is preferable. The most preferred is a modified polyolefin in which an isocyanate group-containing unsaturated compound is grafted onto the polyolefin by the above-mentioned modification method in an amount of 0.001 to 1.5 mol% based on the olefin monomer.

The present invention will be described in detail below. (A) Polyolefin The polyolefin used in the laminate of the present invention is an ethylene homopolymer, a propylene homopolymer, a butylene homopolymer, an ethylene / α-olefin copolymer,
Examples thereof include a copolymer of propylene and α-olefin. The molecular weight of these polyolefins is generally 10,000 to 1,000,000, preferably 20,000 to 500,000, and particularly preferably 50,000 to 300,000. These polyolefins are a catalyst system (Ziegler catalyst) obtained from a transition metal compound and an organoaluminum compound, or a chromium compound (eg, chromium oxide) on a carrier (eg, silica).
Can be obtained by homopolymerization or copolymerization of olefins using a catalyst system (Phillips catalyst) obtained by supporting olefin, or a radical initiator (for example, organic peroxide).

(B) Polyalkenyl terephthalate resin The polyalkenyl terephthalate resin used in the laminate of the present invention comprises an ester of an alkenyl glycol such as ethylene glycol, propylene glycol, butylene glycol and terephthalic acid or dimethyl terephthalate as a constituent unit. It is a polymer. Of these, polyethylene terephthalate and polybutylene terephthalate are common because of their ease of production and economy, and they are also used as the preferred resin in the present invention.

(C) Modified polyolefin The modified polyolefin used in the laminate of the present invention is a polyolefin grafted with an isocyanate group-containing unsaturated compound. This will be described below. (A) The polyolefin used for modifying the polyolefin is the same as the polyolefin constituting the above-mentioned laminate. The shape of the polyolefin may be either powder or pellets, but from the viewpoint of enhancing dispersibility and modification efficiency, a shape having a large surface area, that is, powder is preferable.

(B) Isocyanate Group-Containing Unsaturated Compound The isocyanate group-containing unsaturated compound used for graft modification of the polyolefin has at least one double bond and at least one isocyanate group (--NC).
It is a compound containing O). Specifically, (meth) acryloyl isocyanate, crotoyl isocyanate,
Crotonic acid isocyanato ethyl ester, crotonic acid isocyanato butyl ester, (meth) acrylic acid isocyanato ethyl ester, (meth) acrylic acid isocyanato butyl ester, (meth) acrylic acid isocyanato hexyl ester, (meth) acrylic acid isocyanate Examples thereof include nato octyl ester, (meth) acrylic acid isocyanato lauryl ester, and (meth) acrylic acid isocyanato hexadecyl ester, with (meth) acrylic acid isocyanatoethyl ester being particularly preferable.

The modified polyolefin in the present invention is the above-mentioned polyolefin grafted with this isocyanate group-containing unsaturated compound, and the grafting ratio thereof is preferably 0.001 to 1.5 mol% based on the olefin monomer. If the grafting ratio is less than 0.001 mol%, the modified polyolefin will not have sufficient adhesiveness. If it exceeds 1.5 mol%, not only will the physical properties inherent in the polyolefin be impaired, but also the grafted isocyanate Since the nato group is excessive, sufficient adhesiveness cannot be obtained due to deactivation of the isocyanate group during long-term storage.

This modified polyolefin is generally produced by the following method using an organic peroxide as a radical generating initiator. (C) The organic peroxide used as the organic peroxide radical generation initiator is
One with a half-life of 1 to 100-280 ° C is desirable,
Especially, the one having a temperature of 120 to 230 ° C. is preferable. Typical examples of organic peroxides include t-butylperoxybenzoate, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, and di-t-butylperoxide. These organic peroxides may be used alone or in combination of two or more.

(D) The blending amount of the unsaturated group-containing unsaturated compound with respect to 100 parts by weight of the polyolefin at the time of graft modification is 0.01 to 10 parts by weight, preferably 0.02 to 5 parts by weight, and 0.05. -5 parts by weight are particularly preferred. The amount of the unsaturated compound containing an isocyanate group added to 100 parts by weight of the polyolefin was 0.1.
If it is less than 01 parts by weight, the modified polyolefin has poor adhesion. On the other hand, if the amount exceeds 10 parts by weight, the graft reaction efficiency decreases, and unreacted or by-product homopolymerized isocyanate group-containing unsaturated compound remains considerably in the modified polyolefin, resulting in poor adhesion. Not only that, but the physical properties originally possessed by the polyolefin are impaired.

The blending amount of the organic peroxide with respect to 100 parts by weight of the polyolefin is 0.001 to 0.18 parts by weight, preferably 0.01 to 0.18 parts by weight, and more preferably 0.02 to 0. 15 parts by weight is preferred. When the content of the organic peroxide is less than 0.001 part by weight based on 100 parts by weight of the polyolefin, the modified polyolefin has poor adhesion. On the other hand, if the amount exceeds 0.18 parts by weight, not only the physical properties originally possessed by the polyolefin are impaired, but also the graft reaction efficiency decreases, so that unreacted or by-product homopolymerized isocyanate group-containing unsaturated Adhesion is reduced because the compound remains significantly in the modified polyolefin.

(E) Grafting Method (Modification Method) The modified polyolefin of the present invention can be obtained, for example, by using an extruder used in the field of general synthetic resins and carrying out modification while melt-kneading. On this occasion,
The extruder used may be either a non-vent type or a vent type, but from the viewpoint of removing unreacted or by-product homopolymerized isocyanate group-containing unsaturated compounds and organic peroxide decomposed products. A vented extruder is desirable. The kneading temperature is 140 to 280 ° C, and preferably 180 to 230 ° C, although it varies depending on the types of the polyolefin and the organic peroxide used. Kneading temperature is 140 ℃
If it is less than 1, the denaturation will not be performed well. On the other hand, when the temperature exceeds 280 ° C, some of the polyolefin is deteriorated.

The residence time in the extruder is preferably 60 seconds or longer, more preferably 90 seconds or longer. If the residence time in the extruder is less than 60 seconds, satisfactory modification will not occur.
At the time of melt modification, by adding a stabilizer against oxygen or heat generally used in the field of polyolefin, a filler (for example, mica, talc, glass, organic fiber, wood powder), a lubricant and a flame retardant. , May be used as a composite material. The modified polyolefin obtained by the above modification method is one in which an isocyanate group is preferably grafted in an amount of 0.001 to 1.5 mol% based on the olefin monomer, and the melt flow rate thereof is 0.05.
~ 20 g / 10 min. (190 ° C when polyethylene is modified, 230 when polypropylene is modified
C.) is preferred. The isocyanate group grafted to the polyolefin is considered to chemically react with the polyalkenyl terephthalate resin, and enables strong adhesion.

(D) Laminated product The laminated product of the present invention is a modified polyolefin in which (A) a resin layer made of polyolefin and (B) a polyalkenyl terephthalate resin layer are grafted onto (C) polyolefin with an isocyanate group-containing unsaturated compound. The basic structure is a laminate having a three-layer structure adhered by a resin layer. The same resin as the resin used in the laminate of the present invention or another resin may be adhered to these three layers to form a laminate of three or more layers. For example, the (A) resin layer is bonded to the (B) resin layer of the three-layer laminate by the (C) resin layer to form five layers.

With respect to the thickness of each resin layer constituting the laminate, the (C) modified polyolefin resin layer may have a thickness sufficient to maintain the adhesive force, and generally 0.01 to 0.1 m.
m is suitable. The thickness of the (A) polyolefin resin layer and the (B) polyalkenyl terephthalate resin layer is not particularly limited, and an appropriate range is selected depending on the application, but in a normal container or packaging material, the (A) resin layer is 0.01 ~ 3
mm, (B) resin layer is preferably 0.01 to 0.1 mm.

To produce the laminate of the present invention, a molding method as practiced in the field of general synthetic resins,
For example, press molding, hollow molding, film molding, sheet molding, stamping molding and the like may be applied. Typical examples of this molding method include a method of co-extruding a polyolefin resin, a modified polyolefin resin, and a polyalkenyl terephthalate resin with a T-die (multilayer sheet molding), a method of co-extruding a polyolefin resin, a modified polyolefin resin, and a polyalkenyl terephthalate resin. , A method of producing a container by blow molding (multilayer blow molding) or melt extrusion of polyolefin resin, modified polyolefin resin and polyalkenyl terephthalate resin separately to form each thin material (sheet, film), and then each thin Examples include a method of manufacturing a laminated body by adhering objects, and further a method of manufacturing a container by a vacuum forming method, a pressure forming method, or a press forming method.

[0022]

EXAMPLES Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. The used polyolefin resin, modified polyolefin resin, polyethylene terephthalate resin, polybutylene terephthalate resin, and the method for measuring peel strength are as follows. Polyolefin resin (HDPE) Melt flow rate 1.0g / 10min (JIS-
According to K-6760. The load is 2.06 kg,
Linear high-density polyethylene with a density of 0.945 g / cm ³ (Showa Super Co., Ltd .: 4
551H) was used. Polyethylene terephthalate resin (PET) A polyethylene terephthalate film (Lumirror manufactured by Toray Industries, Inc.) subjected to a biaxial stretching process was used. Polybutylene terephthalate resin (PBT) A polybutylene terephthalate film (manufactured by Toray Industries, Inc.) subjected to a biaxial stretching process was used.

Modified polyolefin resin (GPE-1) has a melt flow rate of 1.0 g / 10 m.
in (in accordance with JIS-K-6760. The load is 2.
16 kg), with respect to 100 parts by weight of linear high-density polyethylene having a density of 0.945 g / cm ³ , 1.5 parts by weight of methacrylic acid isocyanate ethyl ester,
0.15 parts by weight of 2,5-dimethyl-2,5-di (t-butylperoxy) hexane was previously mixed using a Henschel mixer, and the resulting mixture was mixed with a 40 mmφ single screw extruder to obtain a resin temperature. Melted and kneaded at 220 ° C. to obtain modified polyethylene grafted with methacrylic acid isocyanatoethyl ester. This modified polyethylene (GPE
-1) has a melt flow rate of 0.2 g / 10 min
Met. The grafting rate was 0.2 mol% with respect to the number of moles of ethylene monomer.

(GPE-2) The melt flow rate is 1.
0 g / 10 min (according to JIS-K-6760. The load is 2.16 kg) and the density is 0.945 g / c.
relative linear high density polyethylene 100 parts by weight is m ^3, 1.5 parts by weight methacrylic acid isocyanate ethyl ester, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane 3 0.0 parts by weight was previously mixed using a Henschel mixer, and the resulting mixture was mixed with 40 mm.
Using a φ single screw extruder, melt kneading was performed at a resin temperature of 220 ° C. to obtain a modified polyethylene grafted with methacrylic acid isocyanatoethyl ester. In this modified polyethylene (GPE-2), gelation occurred due to excess organic peroxide, and the melt flow rate was too small to be measured.

(GPE-3) Melt flow rate is 1.0 g / 10 min (JIS-
According to K-6760. The load is 2.16 kg,
0.3 part by weight of maleic anhydride and 2,5-dimethyl-2,5-di (t-butylperoxy) based on 100 parts by weight of linear high-density polyethylene having a density of 0.945 g / cm ^3. 0.01 parts by weight of hexane was previously mixed using a Henschel mixer, and the resulting mixture was melt-kneaded at a resin temperature of 270 ° C. using a 40 mmφ single screw extruder to obtain a modified polyethylene grafted with maleic anhydride. . This modified polyethylene (GPE-3) had a melt flow rate of 0.5 g / 10 min.

(GPE-4) Melt flow rate is 5.
0 g / 10 min (according to JIS-K-6760. The load is 2.16 kg) and the density is 0.945 g / c.
0.6 parts by weight of glycidyl methacrylate, 2.5 parts by weight per 100 parts by weight of linear high-density polyethylene having m ³
-Dimethyl-2,5-di (t-butylperoxy) hexane (0.04 parts by weight) was mixed in advance with a Henschel mixer, and the resulting mixture was mixed with a 40 mmφ single screw extruder at a resin temperature of 250 ° C. After melt-kneading, unreacted and homopolymerized glycidyl methacrylate was washed away with acetone to obtain a modified polyethylene grafted with glycidyl methacrylate. This modified polyethylene (GPE-4) has a melt flow rate of 2.
It was 8 g / 10 min.

Method of Measuring Peel Strength Test pieces for adhesion peeling test used in the following Examples and Comparative Examples were prepared by heating a polyolefin resin and a modified polyolefin resin at 190 ° C. for 300 seconds with a hot press molding machine.
After producing a monolayer sheet having a thickness of 1 mm under a molding condition of a pressure of 60 kg / cm ² , the above-mentioned two monolayer sheets are laminated with a film of polyethylene terephthalate or polybutylene terephthalate, and various conditions are applied by a heat press molding machine. The one bonded below was cut into a width of 10 mm to obtain a laminated test piece. The peel strength was 10 at the speed of 50 mm / min at the interface between the modified polyolefin resin layer and the polyethylene terephthalate or polybutylene terephthalate resin layer.
The mm-width laminated test piece was measured by the T-type peeling method using a tensile tester.

(Example 1) Polyolefin resin (HDP
E), a modified polyolefin resin (GPE-1) and a polyethylene terephthalate resin (PET) laminated test piece were produced by a hot press molding machine under the conditions of an adhesion temperature of 160 ° C., an adhesion time of 180 seconds and a pressure of 10 kg / cm ^2. did.
The peel strength was good as shown in Table 1.

(Example 2) Polyolefin resin (HDP
E), the modified polyolefin resin (GPE-1) and the polybutylene terephthalate resin (PBT) laminated test pieces were bonded by a hot press molding machine under the conditions of an adhesion temperature of 160 ° C., an adhesion time of 180 seconds and a pressure of 10 kg / cm ² . It was made.
The peel strength was good as shown in Table 2.

Comparative Examples 1 to 3 As modified polyolefin resins, GPE-2, GPE-3, in place of GPE-1,
GPE-4 is used and polyolefin resin (HDP
E), a laminated test piece of polyethylene terephthalate resin (PET) was produced by a hot press molding machine under the conditions of 160 ° C., heating time of 180 seconds and E pressure of 10 kg / cm ² , but the peel strength was As shown in 1, all were low.

Comparative Examples 4 to 6 As modified polyolefin resins, GPE-2, GPE-3, in place of GPE-1,
GPE-4 is used and polyolefin resin (HDP
E), a laminated test piece with a polybutylene terephthalate resin (PBT) was produced by a hot press molding machine under the conditions of 160 ° C., a heating time of 180 seconds and an E pressure of 10 kg / cm ² , but the peel strength was As shown in Table 2, all were low.

[0032]

[Table 1]

[0033]

[Table 2]

[0034]

The laminate of the present invention has a tough melt adhesive property at a low temperature in a short time at the interface between the modified polyolefin and the polyalkenyl terephthalate resin such as polypolyethylene terephthalate and polybutylene terephthalate. Such a laminate is useful as a multi-layer container and a multi-layer packaging material which require chemical resistance, gas barrier property and liquid barrier property.

─────────────────────────────────────────────────── --- Continuation of the front page (56) Reference JP-A-60-162643 (JP, A) JP-A-1-319507 (JP, A) JP-A-8-301944 (JP, A) JP-A-9- 76432 (JP, A) JP-A-9-76430 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) B32B 1/00-35/00 C09J 123/00-123/36

Claims (4)

(57) [Claims] 1. A resin layer comprising (A) a polyolefin and (B) a polyalkenyl terephthalate resin layer (C).
A laminate obtained by adhering a modified polyolefin resin layer obtained by grafting an unsaturated compound containing an isocyanate group onto polyolefin. 2. The laminate according to claim 1, wherein the polyalkenyl terephthalate resin is a polyethylene terephthalate resin or a polybutylene terephthalate resin. 3. The laminate according to claim 1 or 2, wherein the modified polyolefin resin layer is a polyolefin grafted with an isocyanate group-containing unsaturated compound in an amount of 0.001 to 1.5 mol% based on the olefin monomer. body. 4. The modified polyolefin resin layer comprises (a) 100 parts by weight of polyolefin, (b) 0.01 to 10 parts by weight of an isocyanate group-containing unsaturated compound, and (c) 0.001 to 0. A mixture comprising 18 parts by weight of a mixture which is melt-reacted to graft the above-mentioned unsaturated compound containing an isocyanate group to a polyolefin.
The laminated body according to any one of 3 above.