JP7410758B2 - Adhesive resin composition, adhesive resin molded body, adhesive resin laminate, and housing sealing material - Google Patents

Description

The present invention relates to an adhesive resin composition, an adhesive resin molded article, an adhesive resin laminate, and a housing sealant.

Compared to inorganic materials such as metals and glass, organic materials such as resins and rubber have larger gaps between polymer molecules and tend to have lower gas barrier properties against oxygen and other gases. For this reason, gas barrier materials are used to provide gas barrier properties. For example, Patent Document 1 describes applying a coating agent in which inorganic filler fine particles are dispersed in ethylene vinyl alcohol copolymer (EVOH) to a plastic film. It is also described that an inorganic vapor deposited layer and an inorganic filler-containing layer are sequentially laminated on a polyethylene naphthalate film via a transparent primer layer.

Japanese Patent Application Publication No. 2007-211038 Patent No. 5092421

However, in Patent Documents 1 and 2, there is no suggestion whatsoever regarding a resin film that has both adhesive properties and gas barrier properties.

The present invention has been made in view of the above circumstances, and provides an adhesive resin composition having both adhesive properties and gas barrier properties, an adhesive resin molded article, an adhesive resin laminate, a manufacturing method thereof, and a housing. The objective is to provide a sealing material.

In order to solve the above problems, the present invention provides an adhesive resin composition comprising as essential components an acid-modified polyolefin resin (A) and a gas-barrier resin (B) as a gas-barrier component, The density of the polyolefin resin (A) is within the range of 0.8 to 1.0 g/cm ³ , and the density of the gas barrier resin (B) is within the range of 1.1 to 1.5 g/cm ³ . , an adhesive resin composition characterized in that the adhesive resin composition contains the gas barrier resin (B) in a range of 10 to 40 parts by weight based on 100 parts by weight of total solid content. do.

The gas barrier resin (B) may be at least one selected from the group consisting of polyamide resins and polyester resins.
The adhesive resin composition may contain the acid-modified polyolefin resin (A) in an amount of 50 to 90 parts by weight based on 100 parts by weight of the total solid content.
The adhesive resin composition may contain a thermoplastic elastomer resin (C) in an amount of 1 to 15 parts by weight based on 100 parts by weight of the total solid content.

The present invention also provides an adhesive resin molded article, which is characterized by being made of an adhesive resin film or an adhesive resin sheet formed from the adhesive resin composition.
The present invention also provides an adhesive resin laminate comprising an adhesive resin film or an adhesive resin sheet having an adhesive resin layer made of the adhesive resin composition on at least one side of a base layer. provide.
Further, the present invention provides a housing sealing material, characterized in that it is formed from the adhesive resin molded article.
Further, the present invention provides a housing sealing material characterized by being formed from the adhesive resin laminate.

According to the present invention, it is possible to provide an adhesive resin composition, an adhesive resin molded article, an adhesive resin laminate, and a housing sealing material that have both adhesive properties and gas barrier properties.

FIG. 1 is a sectional view showing an example of an adhesive resin molded article of the present invention. FIG. 1 is a cross-sectional view showing an example of an adhesive resin laminate of the present invention. FIG. 2 is a cross-sectional view showing an example of a casing sealed using the casing sealing material of the present invention. FIG. 3 is an explanatory diagram of a method for measuring adhesive strength, and is a perspective view showing (a) a method for preparing a test piece, (b) a test piece, and (c) a method for measuring, respectively.

The present invention will be described below based on preferred embodiments.
The adhesive resin composition of the embodiment is an adhesive resin composition containing as essential components an acid-modified polyolefin resin (A) and a gas barrier resin (B) as a gas barrier component.

[Acid-modified polyolefin resin (A)]
The acid-modified polyolefin resin (A) is a polyolefin resin modified with an unsaturated carboxylic acid or a derivative thereof, and has a carboxyl group or a carboxylic anhydride group in the polyolefin resin. Preferably, the polyolefin resin is modified with an unsaturated carboxylic acid or a derivative thereof. Acid modification methods for acid-modified polyolefin resins include graft modification, such as melt-kneading acid-functional group-containing monomers with polyolefin resins in the presence of radical polymerization initiators such as organic peroxides and aliphatic azo compounds, and acid-functional Examples include copolymerization of group-containing monomers and olefins.

Examples of the polyolefins include polyethylene, polypropylene, poly-1-butene, polyisobutylene, random copolymers of propylene and ethylene or α-olefin, and block copolymers of propylene and ethylene or α-olefin. . Among these, polypropylene resins such as homopolypropylene (homoPP, propylene homopolymer), propylene-ethylene block copolymer (block PP), and propylene-ethylene random copolymer (random PP) are preferred. In particular, random PP is preferred.
Examples of the olefins to be copolymerized include olefin monomers such as ethylene, propylene, 1-butene, isobutylene, 1-hexene, and α-olefin.

The acid functional group-containing monomer is a compound having an ethylenic double bond and a carboxylic acid group or a carboxylic acid anhydride group in the same molecule, and includes various unsaturated monocarboxylic acids, dicarboxylic acids, or dicarboxylic acids. Consists of acid anhydrides.
Examples of acid functional group-containing monomers having a carboxylic acid group (carboxylic acid group-containing monomers) include acrylic acid, methacrylic acid, maleic acid, nadic acid, fumaric acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, and tetrahydrophthalic acid. and α,β-unsaturated carboxylic acid monomers such as endo-bicyclo[2.2.1]-5-heptene-2,3-dicarboxylic acid (endic acid).
Examples of acid functional group-containing monomers having a carboxylic anhydride group (carboxylic anhydride group-containing monomers) include unsaturated dicarboxylic acids such as maleic anhydride, nadic anhydride, itaconic anhydride, citraconic anhydride, and endic anhydride; Mention may be made of anhydride monomers.
These acid functional group-containing monomers may be used alone or in combination of two or more types in the acid-modified polyolefin resin (A).

Among the acid functional group-containing monomers, carboxylic anhydride group-containing monomers are more preferred, and maleic anhydride is more preferred.
If a part of the acid functional group-containing monomer used for acid modification is unreacted, in order to suppress the adverse effect on adhesive strength, the unreacted acid functional group-containing monomer is removed and acid-modified polyolefin resin ( It is preferable to use it as A).

Regarding the propylene component in the acid-modified polyolefin resin (A), from the viewpoint of heat resistance of the resin, it is preferable that propylene units account for the majority. The majority amount here means that the propylene component is 50% by weight or more based on the acid-modified polyolefin resin (A). Therefore, as the acid-modified polyolefin resin (A), an acid-modified polypropylene resin in which the majority is propylene units is preferred.

[Gas barrier resin (B)]
The gas barrier resin (B) functions as a gas barrier component that imparts gas barrier properties to the adhesive resin composition. The gas barrier resin (B) is not particularly limited, but is preferably selected appropriately from the viewpoints of gas barrier properties of the adhesive resin composition, miscibility with resins such as the acid-modified polyolefin resin (A), etc. .

It is preferable that the gas barrier resin (B) has a higher density than the acid-modified polyolefin resin (A). For example, the density of the acid-modified polyolefin resin (A) is within the range of 0.8 to 1.0 g/cm ³ , and the density of the gas barrier resin (B) is within the range of 1.1 to 1.5 g/cm ³ It is preferable that it be within. Specific examples of the gas barrier resin (B) include at least one selected from polyamide resins and polyester resins.

Polyamide resins include polymers with a structure in which polyamine and polycarboxylic acid are dehydrated and condensed [for example, -(NH-X-NH-CO-Y-CO) _n -], and polymers in which aminocarboxylic acid is dehydrated and condensed. Molecules [for example, -(NH-Z-CO) _m -], polymers with a structure in which polyamine, polycarboxylic acid, and aminocarboxylic acid are condensed [for example, -(NH-X-NH-CO-Y-CO)] _n -(NH-Z-CO) _m -]. Note that, as long as a polymer having the same structure can be obtained, it is also possible to use a polyamide resin synthesized by a reaction other than dehydration condensation, such as ring-opening polymerization of lactams.

Polyester resins include polymers with a structure in which polyol and polycarboxylic acid are dehydrated and condensed [for example, -(O-X-O-CO-Y-CO) _n -], and polymers in which hydroxycarboxylic acid is dehydrated and condensed. Molecules [e.g. -(O-Z-CO) _m -], polymers with a structure in which polyol, polycarboxylic acid and hydroxycarboxylic acid are condensed [e.g. -(O-X-O-CO-Y-CO) _n -(O-Z-CO) _m -]. Note that, as long as a polymer having the same structure can be obtained, it is also possible to use a polyester resin synthesized by a reaction other than dehydration condensation, such as transesterification or ring-opening polymerization of lactones.

In illustrating the chemical structure of polyamide resin or polyester resin, X, Y, and Z are aliphatic or aromatic polyvalent groups. The polyvalent groups X, Y, and Z are not limited to divalent groups, but may be trivalent or higher polyvalent groups. The polyvalent groups X, Y, and Z are, for example, organic groups that may contain hydrocarbon groups such as alkylene groups and phenylene groups, oxygen atoms, nitrogen atoms, and the like. X may be one or more organic groups, Y may be one or more organic groups, and Z may be one or more organic groups. m and n represent the number of units corresponding to the monomer.

The adhesive resin composition preferably contains 10 to 40 parts by weight of the gas barrier resin (B) in 100 parts by weight of the total solid content. Further, the adhesive resin composition preferably contains acid-modified polyolefin resin (A) in a range of 50 to 90 parts by weight per 100 parts by weight of the total solid content.

In order to better and more uniformly disperse the gas barrier resin (B) in the adhesive resin composition, it is preferable to melt and knead the acid-modified polyolefin resin (A) and the gas barrier resin (B). As a melt-kneading device, a single-screw extruder, a multi-screw extruder, a Banbury mixer, a plastomill, a heated roll kneader, etc. can be used. The heating temperature during melt-kneading is preferably selected from within the range of 130 to 300° C. in that the acid-modified polyolefin resin (A) is sufficiently melted and is not thermally decomposed. When the acid-modified polyolefin resin (A) is a polypropylene resin, the kneading temperature is preferably 180 to 300°C, and further preferably 240 to 300°C to improve the dispersibility of the gas barrier resin (B). . The kneading temperature can be measured by a method such as bringing a thermocouple into contact with the adhesive resin composition in a molten state immediately after being extruded from a melt-kneading device. The gas barrier resin (B) may be melted during melt-kneading. When the melting point of the gas barrier resin (B) is higher than the kneading temperature, the gas barrier resin (B) may not be melted and may be dispersed in the form of particles or the like.

During melt-kneading, it is preferable to remove volatile components such as moisture from the apparatus in advance. Further, if volatile components are generated during melt-kneading, it is desirable to discharge them out of the apparatus by degassing or the like. Thereby, foaming can be suppressed when forming an adhesive resin molded body or an adhesive resin layer using the adhesive resin composition.

[Thermoplastic elastomer resin (C)]
The adhesive resin composition may contain a thermoplastic elastomer resin (C). As the thermoplastic elastomer resin (C), styrene elastomer, styrene-butadiene copolymer, epoxy-modified styrene-butadiene copolymer, olefin elastomer, polyester elastomer, styrene-butadiene-styrene block copolymer, styrene-ethylene-propylene-styrene block copolymer, Examples include styrene isoprene butadiene styrene block copolymer, styrene isoprene styrene block copolymer, and the like. When the adhesive resin composition contains a thermoplastic elastomer resin (C), it is preferable to contain the thermoplastic elastomer resin (C) in the range of 1 to 15 parts by weight in 100 parts by weight of the total solid content.

The thermoplastic elastomer resin (C) may be used before melt-kneading as long as it does not react with the acid-modified polyolefin resin (A) or the gas barrier resin (B) under the conditions of melt-kneading the adhesive resin composition. It can also be blended. Furthermore, after melt-kneading the acid-modified polyolefin resin (A) and the gas barrier resin (B), the thermoplastic elastomer resin (C) can be kneaded into the adhesive resin composition.

[Adhesive resin composition]
The adhesive resin composition of the embodiment is obtained by melt-kneading an adhesive resin composition containing as essential components an acid-modified polyolefin resin (A) and a gas barrier resin (B) as a gas barrier component, and then extrusion molding. The method makes it possible to produce adhesive resin layers. The presence of acid functional groups in the acid-modified polyolefin resin (A) provides excellent adhesive strength to various adherends such as metals. By containing the gas barrier resin (B), the adhesive resin composition can have both adhesive properties and gas barrier properties. The adhesive resin composition has a simple composition, and an adhesive resin layer can be easily produced.

Other additives such as a filler, a coloring agent, an antioxidant, an antifoaming agent, a leveling agent, a light absorbing agent, etc. can be appropriately added to the adhesive resin composition. The adhesive resin composition contains no resin components or polymers other than the acid-modified polyolefin resin (A) and gas barrier resin (B) which are essential components, and the thermoplastic elastomer resin (C) which is an optional component. It is possible to configure it without containing any components. The proportion of other solids excluding the acid-modified polyolefin resin (A) and gas barrier resin (B), which are essential components, and the thermoplastic elastomer resin (C), which is an optional component, is 100 parts by weight of the total solid content. Among them, the amount may be 10 parts by weight or less, 5 parts by weight or less, 1 part by weight, etc.

[Adherend]
Examples of adherends that can be bonded using the adhesive resin composition of the embodiment include various adherends such as metal, glass, and plastic. The shape of the adherend is not particularly limited, and examples thereof include a film, a sheet, a plate, a panel, a tray, a rod, a box, a housing, and the like.

Examples of metals include steel, stainless steel, aluminum, copper, nickel, chromium, and alloys thereof. It can also be applied to composite materials that have a metal plating layer on the surface, and the base material for plating in that case is not particularly limited as long as plating is possible, and it can be made of various materials such as metal, glass, and plastic. good.

Examples of the glass include alkali glass, non-alkali glass, and quartz glass.
Plastics include polyolefin resins such as polyethylene and polypropylene; polyamide resins such as nylon; aromatic polyester resins such as polyethylene terephthalate (PET); acrylic resins such as polyacrylonitrile (PAN); vinyl acetate (EVA), Examples include polyvinyl resins such as polyvinyl alcohol (PVA), vinyl alcohol/ethylene copolymer (EVOH), polyvinylidene chloride (PVDC), and polyvinyl chloride (PVC).

[Adhesive resin molded body]
The adhesive resin molded article of the embodiment is a molded article that is formed from the adhesive resin composition and has a shape such as a film or a sheet, and can be used as an adhesive resin film, an adhesive resin sheet, or the like. As shown in FIG. 1, the adhesive resin molded body 10 can be manufactured by melt-kneading the adhesive resin composition and forming it into an adhesive resin layer 11 such as a film or sheet by extrusion molding or the like. is possible. At least one side of the adhesive resin molded body 10 can be bonded to adherends 21 and 22.

The adhesive resin molded body 10 is laminated with an adherend by, for example, the methods listed in (1) to (4) below, and heated, preferably heated and pressurized, to form various adherends. It is possible to bond with
(1) A method of laminating and bonding the adhesive resin molded body 10 on one side of an adherend.
(2) A method of laminating and bonding different adhesive resin moldings on both sides of an adherend.
(3) A method in which separate adherends are laminated and adhered to both sides of an adhesive resin molded body.
(4) A method of alternately laminating and bonding a plurality of adhesive resin molded bodies and a plurality of adherends.

[Adhesive resin laminate]
The adhesive resin laminate of the embodiment is a laminate having an adhesive resin layer made of the adhesive resin composition on at least one side of a base layer. As shown in FIG. 2, the adhesive resin laminate 10A has the adhesive resin layer 11 on one or both sides of the base material layer 12, so that the adhesive resin layer 11 can be used to bond to adherends 21, 22. Can be glued. The base layer 12 does not need to have adhesive properties itself, and is preferably one that can be bonded to the adhesive resin layer 11. Similar to the adherends exemplified above, various base material layers 12 such as metal, glass, and plastic may be used. By using the thin base material layer 12, the adhesive resin laminate 10A can be used as an adhesive resin film, an adhesive resin sheet, or the like.

The adhesive resin laminate can be manufactured by a method of melt-kneading the adhesive resin composition and molding the adhesive resin layer by extrusion molding or the like. When the base material layer is made of a thermoplastic resin, the adhesive resin composition can be extruded by a coextrusion method. It is also possible to extrude the adhesive resin composition by an extrusion lamination method.

When the adhesive resin laminate has the adhesive resin layer on only one side of the base layer, it can be laminated with an adherend by, for example, the method listed in (1) or (2) above. It is possible to adhere to various adherends by heating, preferably by heating and pressurizing.
In addition, when the adhesive resin laminate has the adhesive resin layers on both sides of the base layer, the adhesive resin laminate can be laminated with the adherend by, for example, the methods listed in (1) to (4) above. However, it is possible to adhere to various adherends by heating, preferably by heating and pressurizing.

[Case sealing material]
The case sealing material of the embodiment can be formed from the adhesive resin molded body or the adhesive resin laminate. In FIG. 3, an adhesive resin molded body 10 is placed between adherends 21 and 22 that constitute a housing 20, and the adherends 21 and 22 are bonded together using the adhesive resin molded body 10. , exemplifies a configuration in which the internal space 23 of the casing 20 is sealed from the outside of the casing 20.

When the pair of adherends 21 and 22 constituting the casing 20 are made of metal, glass, etc., since the casing 20 itself has high gas barrier properties, an adhesive resin is used to seal the gap between the adherends 21 and 22. It is preferable that the molded body 10 is thin. Since the adhesive resin composition can be formed into a film even at a thickness of 50 μm, it is possible to prevent the gas barrier properties of the housing 20 from deteriorating in the cross-sectional direction. As the sealing material for the housing 20, it is also possible to use an adhesive resin laminate 10A having adhesive resin layers 11 on both sides of the base layer 12. The width of the housing sealing material along the cross-sectional direction of the housing 20 is not particularly limited, but may be, for example, about 1 to 5 mm.

Although the present invention has been described above based on the preferred embodiments, the present invention is not limited to the above-described embodiments, and various modifications can be made without departing from the gist of the present invention.

The present invention will be specifically described below with reference to Examples.

(Adhesive resin film)
Adhesive resin films of Examples and Comparative Examples were manufactured using the compositions shown in Table 1. To manufacture an adhesive resin film, first, acid-modified polyolefin resin (A), gas barrier resin (B), and thermoplastic elastomer resin (C) are melt-kneaded, and then extrusion molded into a film of a predetermined thickness. It was carried out using the following method. The melt kneading during extrusion molding was carried out at 275° C. for 2 minutes.

The meanings of the abbreviations used in Table 1 are as follows.
"(A)-1": Maleic acid-modified polypropylene (acid addition 0.1% by mass, melting point 140°C, density 0.9g/cm ³ )
"(B)-1": Polyamide 6 (density 1.13 g/cm ³ , melting point 225°C, Amiran (registered trademark) CM1021T, manufactured by Toray Industries, Inc.)
"(B)-2": Polyamide 66 (density 1.14 g/cm ³ , melting point 265°C, Amiran (registered trademark) CM3001N, manufactured by Toray Industries, Inc.)
"(B)-3": MX nylon (density 1.22 g/cm ³ , melting point 237°C, MX nylon S6001, manufactured by Mitsubishi Gas Chemical Co., Ltd.)
"(B)-4": Polyamide 12 (density 1.02 g/cm ³ , melting point 178°C, Diamid (registered trademark) X1743, manufactured by Daicel Evonik Co., Ltd.)
"(B)-5": Polyester (density 1.4 g/cm ³ , melting point 240°C, polyethylene terephthalate (PET))
"(C)-1": Propylene-α-olefin copolymer elastomer (softening point 70°C)

(Method for evaluating film formability)
The appearance of the adhesive resin film obtained by extrusion molding was visually confirmed, and it was evaluated as "○" if there were no problems in appearance, and "x" if defects such as tears or holes occurred due to unevenness.

(Method of measuring adhesive strength)
As shown in FIG. 3(a), a sample of the adhesive resin molded body 10 with a length of 20 mm is sandwiched between test adherends 31 and 32 with a length of 50 mm, and heated as shown in FIG. 3(b). A test piece 30 was prepared by crimping. The width of the test piece 30 was 15 mm. After heat-pressing, the test piece 30 may be cut in the width direction so that the adhesive resin molded body 10 and the test adherends 31 and 32 have the same width. As shown in FIG. 3(c), the test piece 30 is pulled by T-peeling so that the ends of the adhesive resin molded bodies 10 of the test adherends 31 and 32 on the side that are not bonded are approximately 180°. The adhesive strength was measured between the adhesive resin molded body 10 and the test adherends 31 and 32.

The sample of the adhesive resin molded body 10 is an adhesive resin film having a thickness of 50 μm molded from an adhesive resin composition having the composition shown in Table 1. The test adherends 31 and 32 are aluminum foils with a thickness of 40 μm. The heat-press bonding conditions for producing the test piece 30 were a temperature of 150° C., a pressure of 0.1 MPa, and a time of 3 seconds. The measurement conditions for T-shaped peeling were a speed of 300 mm/min and a width of 15 mm. When the adhesive strength was 5 N/15 mm or more, it was evaluated as "○", and when it was less than 5 N/15 mm, it was evaluated as "x".

(Method for measuring oxygen permeability)
In accordance with JIS K 7126-2 (Plastic films and sheets - Gas permeability test method - Part 2: Isobaric method) method A (electrolytic sensor method), temperature: 30°C, humidity: 70% RH, measurement area: 50 cm The oxygen permeability of the adhesive resin film was measured under the measurement conditions of ² . The thickness of the adhesive resin film used for measuring oxygen permeability was 50 μm, the same as the adhesive resin film used for measuring adhesive strength.

When the oxygen permeability of the adhesive resin film was less than 1700 cc/(m ² ·day · atm), it was evaluated as "○", and when it was 1700 cc/(m ² ·day · atm) or more, it was evaluated as "x". Note that due to limitations of the measuring device, when the measured value was 1800 cc/(m ² ·day · atm) or more, the result was displayed as "1800 or more."

Table 2 shows the evaluation results of the adhesive resin film. The adhesive resin films of Examples 1 to 7 have good film formability and have sufficient adhesive strength (adhesiveness) and oxygen permeability (gas barrier properties).
The adhesive resin film of Comparative Example 1 used only the acid-modified polyolefin resin (A) and did not contain the gas barrier resin (B), so it had high oxygen permeability and low gas barrier properties. The adhesive resin film of Comparative Example 2 had poor film formability, no adhesiveness, high oxygen permeability, and low gas barrier properties, probably because the proportion of the gas barrier resin (B) was too high. The adhesive resin film of Comparative Example 3 had high oxygen permeability and poor gas barrier properties, probably because the density of the gas barrier resin (B) was too low or the density difference with the acid-modified polyolefin resin (A) was too small. was low.

DESCRIPTION OF SYMBOLS 10... Adhesive resin molded body, 10A... Adhesive resin laminate, 11... Adhesive resin layer, 12... Base material layer, 20... Housing, 21, 22... Adherent, 23... Internal space of housing, 30...Test piece, 31, 32...Test adherend.

Claims (8)

An adhesive resin composition comprising as essential components an acid-modified polyolefin resin (A) and a gas barrier resin (B) as a gas barrier component,
The density of the acid-modified polyolefin resin (A) is within the range of 0.8 to 1.0 g/cm ³ , and the density of the gas barrier resin (B) is within the range of 1.1 to 1.5 g/cm ³ is within,
An adhesive resin composition characterized in that the adhesive resin composition contains the gas barrier resin (B) in a range of 10 to 40 parts by weight based on 100 parts by weight of total solid content. The adhesive resin composition according to claim 1, wherein the gas barrier resin (B) is at least one selected from the group consisting of polyamide resins and polyester resins. 3. The adhesive resin composition according to claim 1 or 2, wherein the adhesive resin composition contains the acid-modified polyolefin resin (A) in a range of 50 to 90 parts by weight based on 100 parts by weight of the total solid content. Adhesive resin composition. Any one of claims 1 to 3, wherein the adhesive resin composition contains a thermoplastic elastomer resin (C) in a range of 1 to 15 parts by weight based on 100 parts by weight of the total solid content. The adhesive resin composition described in 1. An adhesive resin molded article comprising an adhesive resin film or an adhesive resin sheet formed from the adhesive resin composition according to any one of claims 1 to 4. It is characterized by being made of an adhesive resin film or an adhesive resin sheet having an adhesive resin layer made of the adhesive resin composition according to any one of claims 1 to 4 on at least one side of a base layer. Adhesive resin laminate. A case sealing material formed from the adhesive resin molded article according to claim 5. A case sealing material formed from the adhesive resin laminate according to claim 6.

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