JP3184725B2 - Adhesive resin composition, laminate thereof and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive resin composition having excellent adhesion to polyamide, aluminum foil, particularly polyester, and a laminate thereof.

[0002]

2. Description of the Related Art Polyolefins have excellent heat sealing properties and moisture proof properties and are easy to extrude. Therefore, they are laminated to various types of resin films, aluminum foil, paper, etc., as well as single-layer films, and are used in packaging materials. Widely used. However, polyolefins such as polyethylene are non-polar, and have polyamides, polyesters,
It is difficult to directly adhere to aluminum foil or the like due to poor adhesiveness. At present, a method of applying an adhesive such as an anchor coat agent is generally used.

[0003] The current bonding method using an anchor coating agent involves a complicated coating process or has a problem in safety and working environment due to the use of an organic solvent. Therefore, there is a strong demand for the development of a direct bonding technology. ing. To solve this, for example, (1) 300 ° C.
A method of extruding polyethylene at the above high temperature, (2)
Ozone treatment (Japanese Patent Application Laid-Open No. 57-157724) and (3) Method of introducing acid anhydride groups, carboxyl groups, etc. into polyolefins (Japanese Patent Application Laid-Open Nos. 57-133055 and 59-157).
No. -75915).

[0004]

However, all of the above methods have insufficient adhesion to polyester, and it has not been possible to directly adhere to polyester by extrusion lamination. In addition, the ozone treatment had problems of odor and corrosion. The present invention has been made in view of such circumstances, and an object of the present invention is to provide an adhesive resin composition having excellent adhesiveness to polyester, and a laminate thereof.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the above object can be achieved by a composition of a specific polyolefin and an epoxy compound. Was completed. That is, the present invention provides (A) a polyolefin resin having at least one functional group selected from the group consisting of an acid anhydride group, a carboxyl group and a carboxylic acid metal salt, and (B) two or more epoxy groups. And the molecular weight is 300
(A) Component 1 consisting of an epoxidized vegetable oil of 0 or less
The blending amount of the component (B) is 0.01 to 5 parts by weight based on 00 parts by weight.
The purpose of the present invention is to provide an adhesive resin composition in parts by weight.
Hereinafter, the present invention will be described specifically.

The polyolefin resin (A) in the present invention is a polyolefin resin having in its molecule at least one functional group selected from the group consisting of an acid anhydride group, a carboxyl group and a metal carboxylate. The resin is obtained by copolymerizing an olefin described below with a radical polymerizable monomer having the above functional group in the presence of a radical generator, or by grafting a polyolefin by reacting the radical polymerizable monomer having the above functional group with a polyolefin. Can be obtained by

The olefin used in the former copolymerization method includes ethylene or an α-olefin having 3 to 16 carbon atoms. Further, as the radical polymerizable monomer having the functional group, maleic anhydride, itaconic anhydride,
Examples thereof include citraconic anhydride, (meth) acrylic acid, sodium (meth) acrylate, and zinc (meth) acrylate. The metal carboxylate can also be obtained by adding a metal salt such as sodium carbonate to the carboxyl group-containing polyolefin.

Examples of the raw material polyolefin used for the graft modification include homo- or copolymers of ethylene or α-olefins having 3 to 16 carbon atoms and copolymers of α-olefins and other monomers. Branched low-density polyethylene (hereinafter referred to as “LDPE”), linear low-density polyethylene (hereinafter referred to as “LLDPE”), medium / high-density polyethylene (hereinafter referred to as “HDPE”), polypropylene (with other α-olefins such as ethylene) Including random or block copolymers),
Ethylene - propylene copolymer, ethylene - butene copolymer, ethylene - vinyl acetate copolymer, ethylene - maleic anhydride copolymer, ethylene - maleic anhydride - (meth) and acrylic acid ester terpolymer No.

LDPE is generally obtained by polymerization under a high pressure of 1000 to 3500 atm in the presence of a radical generator such as peroxide, and is characterized by having many long-chain branches. HDPE and LLDPE can be generally obtained by homopolymerization of ethylene or copolymerization with another α-olefin using a Ziegler catalyst, a metallocene catalyst, a Phillips catalyst, or the like. Generally medium
It is manufactured by the low-pressure method, but can also be manufactured by the high-pressure method.
It is manufactured by any method such as a solution method and a slurry method.

As a graft modification method, a conventionally known technique of melt-kneading a radical generator such as an organic peroxide and the radical polymerizable monomer may be used. The content of the functional group in the polyolefin resin of the present invention is 0.05 to 20% by weight based on the modified monomer,
0.1 to 10% by weight is preferable, and 0.2 to 5% by weight is particularly preferable.

Specific examples of the polyolefin resin of the present invention include ethylene-maleic anhydride copolymer, ethylene-itaconic anhydride copolymer, ethylene-citraconic anhydride copolymer, and ethylene- (meth) acrylic acid copolymer. Polymer,
Ethylene- (meth) acrylic acid sodium salt copolymer,
Ethylene-maleic anhydride- (meth) acrylate copolymer, ethylene-maleic anhydride-vinyl alcohol ester copolymer, maleic anhydride-modified polyethylene, maleic anhydride-modified polypropylene, maleic anhydride-modified ethylene- (meth) Acrylic ester copolymers and the like can be mentioned. Among them, ethylene-maleic anhydride copolymer and ethylene-maleic anhydride-
(Meth) acrylic acid ester copolymer is preferred.

The (B) epoxidized plant of the present invention
The crude oil is a compound having two or more epoxy groups (oxirane groups) in the molecule and having a molecular weight of 3000 or less.
Examples of epoxidized vegetable oils, e epoxidized soybean oil, epoxidized olive oil, epoxidized safflower oil,
Epoxidized corn oil, etc. epoxidized linseed oil. These are obtained by epoxidation with an unsaturated double bond of natural vegetable oils such as peracetic acid, O-130P as commercial products for example by Asahi Denka Co. (epoxidized soybean oil), O-180A (Epoxidized linseed oil).

The non-epoxidized or insufficiently epoxidized oil, which is a by-product of epoxidizing vegetable oil, does not hinder the gist and essence of the present invention. The third component may be mixed in the composition. The molecular weight of the epoxy compound in the present invention needs to be 3000 or less, and preferably 1500 or less. Molecular weight 3000
If it exceeds, the adhesive strength becomes insufficient.

The amount of component (B) in the composition of the present invention is 0.01 to 5% by weight, preferably 0.05 to 2% by weight, based on 100 parts by weight of component (A). When the composition ratio is less than 0.01% by weight, the adhesive strength is not sufficiently improved, and when the composition ratio exceeds 5% by weight, a problem of odor is generated, which is not preferable.

The adhesive composition of the present invention is a composition comprising the component (A) and the component (B) and has excellent adhesive properties. However, by blending a specific polyolefin, the adhesive composition can maintain its adhesive performance. Workability can be dramatically improved. The (C) polyolefin to be blended has a melt flow rate (hereinafter, referred to as “MFR”) of 0.1 to 30 g / 10 min, preferably 1 to 15 g / 10 min.
Need to be minutes. When the MFR is less than 0.1 g / 10 minutes, high-speed moldability and thin-wall moldability are inferior. On the other hand, 30g
If the heating time exceeds / 10 minutes, the heat seal strength and the neck-in characteristics are undesirably reduced. As the polyolefin, the raw material polyolefin used for the graft modification can be used. Among these, a branched low-density polyethylene is preferable. The mixing ratio of the component (C) is the same as the component (A) and the component (C).
At most 70% by weight with respect to the total amount of
% By weight or less is preferred. When the compounding ratio of the component (C) exceeds 70% by weight, the heat-sensitive adhesive strength tends to decrease. When the component (C) is blended, the blending amount of the component (B) is 0.01 to 5 parts by weight based on 100 parts by weight of the total amount of the components (A) and (C).

The composition of the present invention can be prepared by a known mixing method,
For example, it can be obtained by mixing using a Henschel mixer, a ribbon mixer, or the like, or by melt-mixing the mixture using an open roll, a kneader, a Banbury mixer, an extruder, or the like. The mixing temperature is usually 160 to 350 ° C, preferably 180 to 280.
° C. The composition obtained can be formed into a film, sheet, tube, container, or the like by using a known melt molding method or compression molding method, and used. Further, the composition of the present invention may optionally contain conventional additives such as a plasticizer, a lubricant, an antioxidant, a heat stabilizer, an antiblocking agent, an antistatic agent, an antistatic agent, a pigment and a filler. It may be added.

Further, the composition of the present invention can be used as a laminate by laminating it on a substrate, taking advantage of its excellent adhesive property. The substrate is not particularly limited, but has excellent adhesion to polyester such as PET and PBT, polyamide, saponified ethylene-vinyl acetate copolymer, and aluminum foil. The shape of the substrate may be any shape such as a film, a sheet, a woven fabric, a nonwoven fabric, a steel plate coated with the above-mentioned material, glass, and ceramics. As the lamination method, a conventionally known method can be used. That is, a method of laminating using a press molding machine, a method of laminating with a roll using a calendaring machine, a method of laminating on a substrate using an extrusion laminator, and simultaneously extruding a substrate using a co-extrusion laminator Lamination method and the like can be mentioned.

[0018]

The present invention will be described in more detail with reference to the following examples. The MFR conforms to JIS K6758,
The measurement was made at a temperature of 190 ° C. for the polyethylene-based resin and at 230 ° C. for the polypropylene-based resin. Adhesive strength is 15
After the test piece having a width of mm was left in a thermostat at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours, the test piece was heated at a speed of 300 mm / min.
° The strength (g) at the time of peeling was measured. The humidification strength was measured by placing the test piece in a thermostat at a temperature of 60 ° C and a relative humidity of 90%.
After standing for 8 hours, the adhesive strength was measured by the above method. Yarn pull-out resistance cuts two warp yarns at the center 70 mm away from the short side of the test piece (20 mm × 170 mm),
Further, a cut is made from both sides of the long side at a distance of 30 mm from the position to the other short side, and the warp yarn 2 at the central portion is cut.
Cut the other warps leaving the book. The test piece was attached to a tensile tester and measured at a tensile speed of 200 mm / min. In the creep peeling test of the welded portion, two strip-shaped test pieces having a width of 30 mm were overlapped with each other by 50 mm in the longitudinal direction, and the overlapped portions were heat-welded to a 20-mm-wide band using a welder. The welded film was left under a condition of a temperature of 40 ° C. for 24 hours while a load of 40 kg was applied, and the presence or absence of cutting was measured.

As the component (A), the following six types of resins (A-1 to A-6) were used. A-1: Ethylene-maleic anhydride copolymer (maleic anhydride content 2.5% by weight, MFR 12 g / 10
Min) A-2: ethylene-maleic anhydride-acrylate terpolymer MFR 10 g / 10 min, melting point 83 ° C) A-3: ethylene-maleic anhydride-acrylate terpolymer MFR 12 g A-4: Ethylene-methacrylic acid copolymer (Nucrel 0908C; manufactured by DuPont-Mitsui Polychemicals) A-5: Ionomer (Himilan H1605; Mitsui)
A-6: Maleic anhydride-grafted polypropylene (Adtex ER320P; manufactured by Showa Denko KK) As the component (B), the following two types (B-1 to B- 2 ) were used. B-1: Epoxidized soybean oil (O-130P; manufactured by Asahi Denka Kogyo Co., Ltd.) B-2: Epoxidized linseed oil (O-180A; manufactured by Asahi Denka Kogyo Co., Ltd.) (C) As the components, the following two types (C) -1 to C-2) were used. C-1: Low-density polyethylene (SHOWLEX L18
2; Showa Denko KK) MFR 8 g / 10 min, density 0.918 g / cm ³ C-2: polypropylene (show aroma LR510;
(Showa Denko KK) MFR 14g / 10min

Further, as a base material, a polyester film (12 μm), a polyester base fabric (thickness 750 d, number of shots 20 × 23 / square inch) and polyamide 6
Six films (15 μm) were used. Polyester coated color iron plate (Yodocolor F104)
1, Yodogawa Steel Works).

Examples 1 to 9 and Comparative Examples 1 to 10 Table 1 shows the types and blending amounts (A) and (B).
The component (C) and the component (C) were dry-blended with a Henschel mixer, and then pelletized using an extruder (KTX-30, manufactured by Kobe Steel Ltd.). The MFR of each of the obtained pellets was measured. The pellets were laminated on a substrate (polyester film and polyamide film) at a thickness of 25 μm using a 90 mmφ extrusion lamination molding machine (manufactured by Modern Machinery) at a resin temperature of 300 ° C. and a lamination speed of 200 mm / min. At that time, sanding was performed with a 60 μm-thick LLDPE film for reinforcement in a peeling test. With respect to the obtained film, the adhesive strength at the interface between the resin composition of the present invention and the substrate was measured. Table 1 shows the above results.

[0022]

[Table 1]

Example 10 Using a polyester base fabric as a base material, component (A) (A-3)
A composition consisting of 100 parts by weight and 1.0 part by weight of the component (B) (B-1) was laminated on both surfaces of the base fabric in a thickness of 250 μm by extrusion lamination. The obtained laminate was measured for a yarn pull-out resistance and a creep peeling test at a welded portion.
Table 2 shows the results.

Comparative Example 11 (A) Example 10 except that only the component (A-3) was used.
A laminate was prepared and evaluated in the same manner as described above. Table 2 shows the results.

[0025]

[Table 2]

Example 11 and Comparative Example 12 A film having a thickness of 75 μm was prepared from the compositions used in Example 10 and Comparative Example 11 using a T-die molding machine.
The film is sandwiched between a color iron plate (25 mm × 125 mm, thickness 0.6 mm) and a 5 mm-thick rock wool (Roofen L; manufactured by Nitto Boken Kogyo), and a spacer (thickness) for preventing crushing. : 3.5mm) and put it on a thermal press molding machine.
And pressed under a condition of a sample surface pressure of 1 kg / cm ² for 3 seconds to obtain a laminate. Initially for the laminate,
After treatment under three conditions of immersion in 60 ° C warm water for 1 hour and immersion in 60 ° C warm water for 4 hours, the peeled state was evaluated by peeling by hand. As a result of evaluation, all the laminates using the composition of Example 10 were broken.

On the other hand, in the laminate using the composition of Comparative Example 11, the material was broken at the beginning, but the interface was broken after immersion in 60 ° C. hot water for 1 hour, and the heat-bonded portion was immersed in 60 ° C. hot water for 4 hours. Uplift was observed on the entire surface.

[0028]

The resin composition of the present invention is particularly useful as a laminate because it has excellent adhesion to polyester.

────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI (C09J 123/26 163: 00) (72) Inventor Mahiro Ueno 3-2 Chidoricho, Kawasaki-ku, Kawasaki-shi, Kanagawa Showa Denko KK In Kawasaki Resin Laboratory (72) Inventor Naoki Mihokawa 3-2 Chidori-cho, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture Showa Denko KK Kawasaki Resin Laboratory (56) References JP-A-1-126356 (JP, A) JP-A Sho 63-56520 (JP, A) JP-A-56-136833 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 23/26 C09J 123/26 B32B 27/08

Claims (9)

(57) [Claims] 1. A polyolefin resin having at least one functional group selected from the group consisting of (A) an acid anhydride group, a carboxyl group, and a carboxylic acid metal salt, and (B) two or more epoxy groups. And the molecular weight is 300
(A) Component 1 consisting of an epoxidized vegetable oil of 0 or less
The blending amount of the component (B) is 0.01 to 5 parts by weight based on 00 parts by weight.
An adhesive resin composition which is part by weight. 2. The composition comprising (A) a polyolefin resin, (B) an epoxidized vegetable oil, and (C) a polyolefin having a melt flow rate of 0.1 to 30 g / 10 min. (C) of the total amount of components
An adhesive resin in which the composition ratio of the component is at most 70% by weight, and the blending amount of the component (B) is 0.01 to 5 parts by weight based on 100 parts by weight of the total amount of the components (A) and (C). Composition. 3. The adhesive resin according to claim 1, wherein (A) the polyolefin resin is an ethylene-maleic anhydride copolymer or an ethylene-maleic anhydride- (meth) acrylate copolymer. Composition. 4. The adhesive resin composition according to claim 2, wherein (C) the polyolefin is a branched low-density polyethylene. 5. A laminating composition comprising the adhesive resin composition according to any one of claims 1 to 4 . 6. a layer comprising the adhesive resin composition according to any one of claims 1-4, comprising at least two layers of the base layer laminate. 7. The laminate according to claim 6 , wherein the base material layer directly contacts the layer made of the adhesive resin composition. 8. The laminate according to claim 6 , wherein the base material layer is made of polyester, polyamide, or aluminum foil. 9. The method for producing a laminate according to claim 6 , wherein the method for bonding the adhesive resin composition to the substrate is any one of extrusion lamination, heat-sensitive bonding, and calendaring. .