JP2002249754A - Resin composition for adhesive and laminated material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition for an adhesive having an excellent heat resistance, adhesion and forming property as the adhesive for bonding a thermotropic liquid crystal polymer layer with a polyolefin layer, and a laminated material of the thermotropic liquid crystal polymer layer with the polyolefin layer, excellent in forming property and barrier property by using the above resin composition for the adhesive. SOLUTION: This resin composition for the adhesive is obtained by containing (A) the thermotropic liquid crystal polymer and (B) the polyolefin, and the resin composition for the adhesive is also obtained by containing (C) an polyarylate or (D) a copolymer of an unsaturated carboxylic acid or its derivative with the polyolefin in addition to the above components. The laminated material consisting of the thermotropic liquid crystal polymer layer and the polyolefin layer is also provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for an adhesive which is excellent in bonding a laminate comprising a thermotropic liquid crystal polymer and a polyolefin, and to a laminate of a thermotropic liquid crystal polymer and a polyolefin using the same.

[0002]

2. Description of the Related Art As a film having a gas barrier property, a multilayer film using an ethylene vinyl alcohol copolymer (EVOH) or polyvinyl alcohol (PVA) is widely used as a food packaging material, a preservation packaging material and the like. . In a resin gasoline tank, a multilayer material of polyethylene and EVOH is used. The polyethylene has a shape and mechanical strength, and the transmission of gasoline vapor is prevented by EVOH within a practical range.

Also, polyethylene terephthalate is widely used for plastic bottles and the like because of its relatively excellent gas barrier properties and low cost. On the other hand, liquid crystal polymers have excellent gas barrier properties,
Since EVOH has a barrier property against water vapor having no barrier property and has an advantage that the structure of a multilayer sheet can be simplified, its application research is progressing.

However, a liquid crystal polymer has a specific high self-alignment property, and a thermotropic liquid crystal polymer has a high crystallization rate, so that it is easily solidified, has a low weld strength in injection molding, and has a high heat fusion property with other materials. Is also extremely bad. Therefore, several proposals have been made on adhesives for the purpose of improving the adhesion between the thermotropic liquid crystal polymer and other materials.

For example, glycidyl-modified ethylene vinyl acetate is used to improve the adhesion between the thermotropic liquid crystal polymer and polybutylene terephthalate, and ethyl acrylate-ethylene-maleic anhydride is used to improve the adhesion to polypropylene. JP-A-2-
253950 JP, JP-A-2-253951, JP-A-4-135750
There is an official gazette.

[0006] Japanese Patent Application Laid-Open No. H11-240074 discloses an ethylene-glycidyl methacrylate copolymer for improving the adhesion to polyethylene. But,
All of the adhesives had inferior heat resistance as compared with the thermotropic liquid crystal polymer, and had disadvantages of poor moldability because the melt viscosity was not sufficiently high.

[0007]

The problem to be solved by the present invention is to provide an adhesive for bonding a thermotropic liquid crystal polymer layer and a polyolefin layer with excellent heat resistance,
An object of the present invention is to provide a resin composition for an adhesive having adhesive properties and moldability, and a laminate of a thermotropic liquid crystal polymer layer and a polyolefin layer having excellent moldability and barrier properties using the resin composition for an adhesive. .

[0008]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, when forming a multilayer film composed of a thermotropic liquid crystal polymer and a polyolefin, as an intermediate layer formed between both layers, By using a resin composition for an adhesive containing the thermotropic liquid crystal polymer and the polyolefin, excellent adhesiveness,
The inventors have found that a multilayer film excellent in moldability is formed, and have completed the present invention.

That is, the present invention is a resin composition for an adhesive comprising (A) a thermotropic liquid crystal polymer and (B) a polyolefin, and preferably comprises (A) a thermotropic liquid crystal polymer and (B) a polyolefin. A resin composition for an adhesive, which further comprises (C) a polyarylate or (D) a copolymer of an unsaturated carboxylic acid or a derivative thereof and a polyolefin, and which has a melt viscosity of 100
(Pa · s) or more is preferable.

Among them, the preferred polyarylate (C) is a polyester having a structure represented by the general formula (1):

General formula (1)

Embedded image

(Wherein, R is a hydrogen atom or an alkyl group of C _m H _{2m + 1} , m represents an integer of 1 to 8) Further, the aromatic dicarboxylic acid component of the polyarylate is isophthalic acid 5 to 100% by mole, 95 to 0% by mole of terephthalic acid, a resin composition for an adhesive wherein R of the general formula (1) is a methyl group, and (D) an unsaturated carboxylic acid or a derivative thereof and a polyolefin. Is a resin composition for an adhesive, wherein the graft amount of the unsaturated carboxylic acid or its derivative is 0.01 to 10% by weight.

Further, the resin composition for an adhesive of the present invention comprises (A)
The weight ratio of the thermotropic liquid crystal polymer to the (B) polyolefin is preferably from 10/90 to 90/10, and further the (C) polyarylate is preferably from 10/90 to 90/90.
(D) a resin composition for an adhesive which is added in a weight ratio of 99/1 or (D) in a weight ratio of an unsaturated carboxylic acid or a derivative thereof to a copolymer of a polyolefin of 10/90 to 99/1. .

The present invention also provides a laminate comprising the adhesive resin composition of the present invention as an adhesive layer between a (I) thermotropic liquid crystal polymer layer and a (II) polyolefin layer, (I) The content of the thermotropic liquid crystal polymer in the adhesive layer (III-1) in contact with the thermotropic liquid crystal polymer layer is higher than that of the polyolefin, and (II) the content of the polyolefin in the adhesive layer (III-2) in contact with the polyolefin layer Include a laminate having two or more adhesive layers than the thermotropic liquid crystal polymer, and a particularly preferred shape of the laminate is a film or a sheet.

[0015]

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a resin composition for an adhesive comprising (A) a thermotropic liquid crystal polymer and (B) a polyolefin, and further comprises (C) a polyarylate or (D) an unsaturated resin. The present invention relates to a resin composition for an adhesive comprising a copolymer of a carboxylic acid or a derivative thereof and a polyolefin, and a laminate comprising a thermotropic liquid crystal polymer layer and a polyolefin layer using the resin composition for an adhesive. is there.

The (A) thermotropic liquid crystal polymer used in the present invention is a polymer exhibiting liquid crystallinity in a temperature range not lower than the melting point of the polymer, and is generally a wholly aromatic polyester or polyesteramide. The monomers that form this are terephthalic acid, isophthalic acid, 1,
4-hydroquinone, resorcinol, 4-aminobenzoic acid, 4-hydroxybenzoic acid,

4-aminophenol, 1,4-phenylenediamine, 4,4'-biphenol, 4,4'-biphenyldicarboxylic acid, 6-hydroxy-2-naphthoic acid, 2,6-naphthalenedicarboxylic acid, 6-dihydroxynaphthalene, 4-aminophenol and the like. A copolymer obtained by copolymerizing one or more of these monomers is used.

Methods for producing these thermotropic liquid crystal polymers are disclosed in, for example, US Pat. No. 4,473,682, US Pat. No. 5,204,443 and US Pat. No. 5,656,714. ing.

The polyolefin (B) used in the present invention is preferably polyethylene or polypropylene, or a random copolymer of ethylene or propylene and an α-olefin. Examples of the α-olefin include propylene having 3 to 10 carbon atoms, 1-butene, and 1-butene.
-Hexene, 4-methyl-1-pentene, 1-octene, 1-decene and the like. There are a number of commercially available polymers, which can be used to advantage.

The adhesive layer of the laminate of the present invention is formed between the thermotropic liquid crystal polymer layer and the polyolefin layer. In general, since a composition composed of a liquid crystal polymer and a polyolefin is a phase-separated system, each component has a co-continuous structure or a sea-island structure similar to the same, so that the thermotropic liquid crystal polymer layer and the polyolefin layer in contact with the adhesive layer are formed. Desirable for even adhesion.

From such a viewpoint, the resin composition used as the adhesive layer is a resin composition containing (A) a thermotropic liquid crystal polymer and (B) a polyolefin, and the weight ratio is 10/90 to 90/10. Is preferably 40/60 to 80/20, and more preferably 50/50 to 70/30.

The adhesive component has a third component for controlling the affinity and viscosity between the thermotropic liquid crystal polymer and the polyolefin and controlling the affinity between the thermotropic liquid crystal polymer layer and the polyolefin layer and the adhesive layer. Alternatively, (C) a polyarylate and / or (D) a copolymer of an unsaturated carboxylic acid or a derivative thereof and a polyolefin may be added.

Here, (A) a resin composition comprising a thermotropic liquid crystal polymer and (B) a polyolefin;
The weight ratio of (C) the polyarylate and / or (D) the copolymer of the unsaturated carboxylic acid or its derivative and the polyolefin is desirably 10/90 to 99/1, preferably 30/70 to 95/5. And more preferably 50/50 to 9
It is 0/10.

[0024] The resin composition can be prepared by a known method. For example, the raw materials are previously mixed by a mixer such as a tumbler or a Henschel mixer, and then mixed with one shaft,
There is a method in which the mixture is supplied to a usual melt-kneading apparatus such as a shaft extruder, a Banbury mixer, a kneader, and a mixing roll, and the mixture is melt-kneaded at a melting temperature of about 200 ° C. to 400 ° C. to form pellets.

The melt viscosities of (A) thermotropic liquid crystal polymer, (B) polyolefin, and (A) and (B) and the adhesive obtained by adding (C) or (D) thereto are as follows. (A) At a temperature 25 ° C. higher than the melting point of the thermotropic liquid crystal polymer, the melt viscosity measured with a capillary rheometer at a shear rate of 5 sec ⁻¹ is 100 (Pa · s) or more, preferably 10 ² to 10 ^7. (Pa · s), more preferably 5 × 10 ²
-10 ⁶ (Pa · s), most preferably 10 ³ -10
⁶ (Pa · s) is used.

At this time, it is difficult to measure the molecular weight of the (A) thermotropic liquid crystal polymer, but the weight average molecular weight of the (B) polyolefin is about 10 ³ to 10 ⁶ . Laminates obtained by coextrusion, multilayer blow molding, etc., are unfavorable in a viscosity range other than those described above, because drawdown, disorder of the multilayer structure, and breakage of the layers are caused to lower the moldability.

In general multi-layer blow molding, the resin of each layer of the laminate is formed into a cylindrical parison by co-extrusion molding of an accumulator system, and then the parison is formed into an arbitrary shape and the temperature is adjusted. It is placed in a mold, and a pressurized gas is blown into a parison and molded. Further, the configuration of the multilayer structure differs depending on the purpose.

For example, in applications that require gas barrier properties such as fuel tanks and barrier properties against solution penetration, (I) a thermotropic liquid crystal polymer layer as a center, (III) an adhesive layer on both sides thereof, and an (II) A polyolefin layer is disposed, and (I) a thermotropic liquid crystal polymer layer and (I)
II) a preferred thickness of the adhesive layer is about 0.01 to 1 mm,
(II) The preferred thickness of the polyolefin layer is about 0.1 to 5
mm.

As the adhesive layer, not only a uniform composition but also a laminate of a plurality of adhesive layers having slightly different resins or resin composition ratios can be used. For example, a resin composition having a high thermotropic liquid crystal content is used as the adhesive layer (III-1) in contact with the thermotropic liquid crystal polymer layer, and a polyolefin resin content is used as the adhesive layer (III-2) in contact with the polyolefin layer. By using a resin composition having a high resin composition, an adhesive layer having two or more resin compositions having improved adhesion to each layer can be effectively used.

That is, by selecting a composition that enhances the affinity of each of the adjacent layers, the adhesive strength between the adhesive layer and the thermotropic liquid crystal polymer layer or polyolefin layer can be increased. Further, it is possible to change the composition continuously and stepwise to have the same effect.

The polyarylate referred to in the present invention is a polyester comprising a dihydric phenol and an aromatic dibasic acid, for example, an aromatic dicarboxylic acid or an ester thereof, an acid anhydride, an acid halide or the like and a bisphenol or an ester thereof. It is obtained by a polycondensation reaction with an acidic derivative.

Examples of these aromatic dicarboxylic acids include isophthalic acid, terephthalic acid, 2,2′-diphenyldicarboxylic acid, 3,3′-diphenyldicarboxylic acid,
4′-diphenyldicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 4,4′-dicarboxydiphenylether, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and the like And preferably 5 to 100 mol% of isophthalic acid and 95 to 0 mol% of terephthalic acid.

Examples of the bisphenol of the present invention include hydroquinone, resorcin, 2,2-bis- (4-hydroxyphenyl) propane, 2,4'-dihydroxydiphenylmethane, bis- (4-hydroxyphenyl) methane, bis- ( 2-hydroxyphenyl) methane, bis-
(4-hydroxy-2,6-dimethyl-3-methoxyphenyl) methane, 1,1-bis- (4-hydroxyphenyl) ethane,

1,2-bis- (4-hydroxyphenyl) ethane, 1,1-bis- (4-hydroxy-2-chlorophenyl) ethane, 2,2-bis- (4-hydroxynaphthyl) propane, 2, 2-bis- (4-hydroxyphenyl) pentane, 3,3-bis- (4-hydroxyphenyl) phenylmethane, para-α, α'-bis-
(4-hydroxyphenyl) -para-diisopropylbenzene, bis- (4-hydroxyphenyl) ether,
4,3'-, 4,2'-, 2,2'-,

2,3'-hydroxydiphenyl ether, 4,4'-dihydroxy-2,6-dimethyldiphenyl ether, bis- (hydroxynaphthyl) ether, bis- (4-hydroxyphenyl) sulfone, bis- (3-hydroxyphenyl) ) Sulfone, 2,4′-dihydroxydiphenyl sulfone and the like. Among them, preferably 3,3 ', 5,5'-tetraalkyl-4,
4′-biphenol, more preferably 3,3 ′, 5
5'-tetramethyl-4,4'-biphenol.

As a polymerization method of polyarylate, an aromatic dicarboxylic acid dihalide and bisphenol are dissolved in two kinds of solvents which are incompatible with each other, and then a two-part solution is prepared in the presence of an alkali and a catalytic amount of a quaternary ammonium salt. Mixed
An interfacial polymerization method in which a polycondensation reaction is carried out by stirring, a solution polymerization method in which an aromatic dicarboxylic acid dihalide and bisphenol are reacted in an organic solvent in the presence of an alkaline compound accepting an acid such as a tertiary amine, an aromatic dicarboxylic acid And a bisphenol diester or an aromatic dicarboxylic acid diester and a bisphenol as a raw material.

The polyarylate of the present invention comprises an aromatic dicarboxylic acid composed of isophthalic acid units and terephthalic acid units, and 3,3 ', 5,5'-tetraalkyl-4,4'-
In the case of a polyester comprising a biphenol unit, particularly a 3,3 ′, 5,5′-tetramethyl-4,4′-biphenol unit, the proportion of isophthalic acid and terephthalic acid constituting the aromatic dicarboxylic acid is as follows: When defined by the amount of isophthalic acid, 5 to 100 mol%, preferably 50 to 10 mol%
0 mol%, more preferably 60 to 100 mol%, and correspondingly 0 to 95 mol% of terephthalic acid units, preferably 0 to 50 mol%, more preferably 0 to 40 mol%.

On the other hand, the ratio of the constituent units of dicarboxylic acid and diol is 50 mol% each. For example, 3,3 ',
Aromatic dicarboxylic acid unit is 50 mol% to 5,5′-tetramethyl-4,4′-biphenol unit 50 mol%.
If it exceeds, a polymer having a high degree of polymerization cannot be obtained, which is not preferred.

The polyarylate used in the present invention has a weight average molecular weight of 2 × in order to maintain high mechanical properties of a molded product.
It is 10 ⁴ or more, preferably about 2 × 10 ⁴ to 1 × 10 ⁶ . Further, the glass transition temperature of the aromatic polyester used in the present invention is preferably from 150 ° C to 400 ° C, more preferably from 200 to 350 ° C, and still more preferably from 200 to 30 ° C.
0 ° C.

(D) The copolymer of an unsaturated carboxylic acid or a derivative thereof and a polyolefin can be obtained by a graft reaction of a monomer selected from an unsaturated carboxylic acid or a derivative thereof to an ethylene / α-olefin copolymer. . The amount of graft modification of the unsaturated carboxylic acid or derivative thereof is usually 0.001 to 15% by weight, preferably 0.01 to 15% by weight.
10% by weight, particularly preferably 0.1 to 5% by weight, of a graft-modified ethylene / α-olefin copolymer is used.

The ethylene / α-olefin copolymer referred to herein means that ethylene and α-olefin are copolymerized at random and have a melt flow rate (ASTM D12).
38. E) is 0.01 to 50 g / 10 min, preferably 0.1 to 50 g / 10 min.
01 to 20 g / 10 minutes, and the ethylene content is 30 to
It is 95 mol%, preferably 75 to 95 mol%, particularly preferably 75 to 90 mol%.

As the α-olefin constituting the ethylene / α-olefin copolymer, one having 3 to 20 carbon atoms is used. Specifically, propylene, 1-butene,
1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-tetradecene, 1-octadecene and the like are used.
Used as a mixture of more than one species.

(D) The unsaturated carboxylic acid or its derivative used in the copolymer of the unsaturated carboxylic acid or its derivative and the polyolefin includes acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid,
Citraconic acid, crotonic acid, isocrotonic acid, endocis-bicyclo (2,2,1) hept-5-ene-2,3
-Unsaturated carboxylic acids such as dicarboxylic acids, and derivatives thereof, for example, acid halides, amides, imides, anhydrides, esters and the like.

Specifically, maleenyl chloride, maleimide,
Examples thereof include maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, and glycidyl maleate. Of these, unsaturated dicarboxylic acids or acid anhydrides thereof are preferred, and in particular, maleic acid, endocis-bicyclo (2,2,1) hept-5-ene-2,
3-Dicarboxylic acids or acid anhydrides thereof are preferably used.

In order to produce a modified product by copolymerizing a modifying monomer selected from the unsaturated carboxylic acids or derivatives thereof with an ethylene / α-olefin copolymer before modification, various known methods can be used. . For example, a method of dissolving an ethylene / α-olefin copolymer in a solvent and then adding a modified monomer to copolymerize, or
After the olefin copolymer is melted, a method of adding a modified monomer and copolymerizing the olefin copolymer may be used.

In any case, the reaction is preferably carried out in the presence of a radical reaction initiator in order to efficiently copolymerize the modified monomer. The grafting reaction is usually performed at a temperature of 60 to 350 ° C. The radical initiator is
It is usually used in an amount of 0.001 to 1 part by weight based on 100 parts by weight of the ethylene / α-olefin copolymer.

Examples of the above radical initiator include organic peroxides, organic peresters and azo compounds. Among them, dicumyl peroxide, di-tert
-Butyl peroxide, 2,5-dimethyl-2,5-di
(tert-Butylperoxy) hexyne-3,2,5-
Dialkyl oxides such as dimethyl-2,5-di (tert-butylperoxy) hexane and 1,4-bis (tert-butylperoxyisopropyl) benzene are preferred.

The copolymer (D) of the unsaturated carboxylic acid or its derivative and the polyolefin to be added to the adhesive layer may be one part diluted with an unmodified polyolefin, for example, an ethylene / α-olefin copolymer. Good.

As the copolymer (D) of the unsaturated carboxylic acid or derivative thereof and the polyolefin used in the present invention, commercially available copolymers can be suitably used. For example, "Admer (trade name, manufactured by Mitsui Chemicals Co., Ltd.)", "Modic (trade name, manufactured by Mitsubishi Chemical Co., Ltd.)", "Bondane (trade name, manufactured by Sumika CFD Chemical Co., Ltd.)" and the like And the like.

A fibrous or granular filler can be added to each resin layer of the laminate of the present invention, if necessary, and usually 1 to 100 parts by weight of the resin component of each layer.
By blending in the range of 100 parts by weight, the strength, rigidity and heat resistance dimensional stability can be further improved.

Examples of the fibrous filler include glass fibers, carbon fibers, silane glass fibers, boron fibers, whiskers such as potassium titanate and zinc oxide, alumina fibers, asbestos, silicon carbide, aramid fibers, ceramic fibers, and the like.
Metal fibers, gypsum fibers and the like can be mentioned.

Examples of the particulate filler include mica, talc, wollastenite, sericite, kaolin, clay,
Silicates such as bentonite, asbestos, alumina silicate and carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, and metal oxides such as alumina, magnesium oxide, silica, zirconia, titania and iron oxide Materials, glass beads, ceramic beads, boron nitride, silicon carbide, calcium phosphate and the like.

Two or more of these may be used in combination or may be hollow. These fillers may be treated with a silane-based or titanium-based coupling agent which is usually used as a filler treating agent. . Further, the adhesive resin composition of the present invention and the resin composition constituting the laminate layer may be any of known and common release agents, coloring agents, heat stabilizers, and ultraviolet stabilizers as long as the effects of the present invention are not impaired. , A foaming agent, a flame retardant, a flame retardant auxiliary, a rust inhibitor, an ultraviolet absorber, an antioxidant, an antistatic agent, and the like.

[0054]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited to these Examples. Unless otherwise specified, “parts” or “%” represents “parts by weight” or “% by weight”.

Reference Example 1: Synthesis of a thermotropic liquid crystal polymer 4-A reaction vessel equipped with a stirring blade and an inlet was placed in a reaction vessel.
Hydroxybenzoic acid 2.8 mol, 2,6-hydroxynaphthoic acid 0.2 mol, terephthalic acid 0.75 mol, 2,
0.25 mol of 6-naphthalenedicarboxylic acid, 0.3 mol of para-aminophenol, 0.67 mol of 4,4′-dihydroxybiphenyl, and 0.03 mol of parahydroxyphenethyl alcohol were charged, and nitrogen was replaced under reduced pressure.
5.5 mol of acetic anhydride was added.

Subsequently, the mixture was heated to 145 ° C. with stirring and reacted for 3 hours.
The reaction was continued under reduced pressure. The obtained crude polymer was pulverized and heated to 290 ° C. over a period of 10 hours under a reduced pressure of 200 Pa to perform solid phase polymerization. The melt viscosity of the obtained polymer was measured using a capillary rheometer at a temperature of 320 ° C. and a shear rate of 5 sec ⁻¹ as 1.2 × 10 ³ (P
a · s), and the melting point was 295 ° C. as measured by a differential scanning calorimeter (DSC) manufactured by Seiko Denshi.

(Reference Example 2: Synthesis of polyarylate) 3,3 ′, 5,5 ′ was added to a polymerization apparatus equipped with a stirring blade and a nitrogen inlet.
-Tetramethyl-4,4'-biphenol 2.41 Kg
(9.8 mol) was added to a solution containing 1.0 kg of sodium hydroxide.
It was dissolved in 0 l of deoxygenated water to obtain an aqueous solution. Separately, 78 g of methyltrioctylammonium chloride, 1.58 Kg (7.8 mol) of isophthalic chloride, and 406 g (2.0 mol) of terephthalic chloride were dissolved in 5 l of deoxygenated toluene to obtain an organic solution.

While stirring the aqueous solution under a nitrogen stream, the organic solution was added, and stirring was continued at 25 ° C. for 30 minutes. Then
The aqueous phase was removed by a gradient method. After repeatedly washing the organic solution phase containing the product with distilled water, it was poured into an acetone bath to obtain a precipitate. The obtained precipitate was repeatedly washed with acetone to obtain an aromatic polyester. Then, in a vacuum dryer, gradually warm from room temperature and finally at 240 ℃ 2 hours,
Vacuum drying was performed at about 200 Pa to obtain 3.5 kg of a polyester resin. When the intrinsic viscosity of this polyester resin was measured in chloroform at 30 ° C., it was 0.97 dl / g.
The weight average molecular weight was 7 × 10 ⁴ .

When the polyester resin was used as a cast film and measured with a dynamic viscoelasticity measuring apparatus manufactured by Seiko Denshi at a temperature rising rate of 1 ° C./min and a frequency of 1 Hz, the glass transition temperature as viewed from the tan δ peak temperature was obtained. Is 27
It was 0 ° C. The tensile strength is 97 MPa and the elastic modulus is 19
It was 00 MPa. The melt viscosity of the obtained polymer is
Using a capillary rheometer, the measured value at 320 ° C. and a shear rate of 5 sec ⁻¹ was 2.4 × 10 ⁵ (Pa ·
s).

(Reference Example 3) The obtained thermotropic liquid crystal polymer and polyethylene (F5010, manufactured by Ace Polymer Co., Ltd.) were each molded into a plate-like specimen (width 10 mm, thickness 2 mm, length 50 mm) using an injection molding machine. Molded into. The obtained polyethylene plate-shaped specimen is referred to as “polyethylene plate-shaped specimen”.

The melt viscosity of this polyethylene was measured using a capillary rheometer at 320 ° C. and a shear rate of 5 sec ^-1.
Was 3.6 × 10 ³ (Pa · s). The plate sample of the thermotropic liquid crystal polymer was further formed into a sheet having a thickness of 0.4 mm by hot pressing, and a strip sample having a width of 10 mm and a length of 50 mm was cut out (hereinafter referred to as “LCP sample”).

(Example 1) The above-mentioned thermotropic liquid crystal polymer and polyethylene were kneaded in an extruder at a weight ratio of 60/40, and this was molded into a plate-shaped specimen by an injection molding machine.
(Width 10 mm, thickness 2 mm, length 50 mm).
The melt viscosity of the kneaded material was measured using a capillary rheometer.
The viscosity at 20 ° C. and a shear rate of 5 sec ⁻¹ is 1.7.
× 10 ³ (Pa · s).

This plate-like specimen was further formed into a sheet having a thickness of 0.1 mm by hot pressing, and a sheet having a width of 10 mm and a length of 5 mm was obtained.
mm strip was cut out and used as an adhesive layer. The LCP test piece and the polyethylene plate-like test piece were overlapped with each other in the longitudinal direction at a width of 5 mm, and the adhesive layer cut into strips was sandwiched between them. Heat fusion was performed for 10 seconds.

Next, a tensile test was performed at a peel angle of 0 ° and a peel speed of 10 mm / min while holding both ends of the bonded product of the obtained LCP specimen and polyethylene plate specimen in a chuck of a tensile tester. The tensile shear strength was determined from the breaking strength, and is shown in Table 1.

Example 2 The above-mentioned thermotropic liquid crystal polymer, polyethylene and polyarylate were used in a weight ratio of 48.
The mixture was kneaded with an extruder at a ratio of / 32/20, and was molded into a plate-like molded sample (width 10 mm, thickness 2 mm, length 50 mm) by an injection molding machine. The melt viscosity of the kneaded product was measured using a capillary rheometer at 320 ° C. and a shear rate of 5 sec ^−1.
Was 2.2 × 10 ³ (Pa · s).

This plate-like specimen was further hot-pressed into a sheet having a thickness of 0.1 mm, and a sheet having a width of 10 mm and a length of 5 mm was obtained.
mm strip was cut out and used as an adhesive layer. Thereafter, a sample piece was molded in the same manner as in Example 1 to determine the tensile shear strength.
It was shown to.

(Example 3) Adomer (SF731, manufactured by Mitsui Chemicals, Inc.), which is a copolymer of the above-mentioned thermotropic liquid crystal polymer, polyethylene and unsaturated carboxylic acid and polyolefin, was mixed at a weight ratio of 70/15/15. And kneaded with an extruder, and this is a plate-shaped specimen
(Width 10 mm, thickness 2 mm, length 50 mm).

The melt viscosity of the kneaded product was 1.5 × 10 ³ (Pa · s) as measured at 320 ° C. at a shear rate of 5 sec ⁻¹ using a capillary rheometer. This plate-like specimen was further formed into a sheet having a thickness of 0.1 mm by hot pressing, and a strip specimen having a width of 10 mm and a length of 5 mm was cut out therefrom to form an adhesive layer. Hereinafter, a sample piece was molded in the same manner as in Example 1, and the tensile shear strength was determined.

Example 4 An adomer (SF731, manufactured by Mitsui Chemicals, Inc.), which is a copolymer of the above-mentioned thermotropic liquid crystal polymer, polyethylene, unsaturated carboxylic acid and polyolefin, was prepared in a weight ratio of 90/5/5 (D1 ), And 60 /
Kneading at a ratio of 25/15 (D2) with each extruder,
This was molded into a plate-like molded specimen (width 10 mm, thickness 2 mm, length 50 mm) by an injection molding machine.

The melt viscosity of the kneaded product was measured using a capillary rheometer at 320 ° C. and a shear rate of 5 sec ⁻¹ , where D1 was 1.3 × 10 ³ (Pa · s) and D2 was 1.
It was 5 × 10 ³ (Pa · s). The plate-shaped specimen was further formed into a sheet having a thickness of 0.1 mm by hot pressing, and a strip specimen having a width of 10 mm and a length of 2.5 mm was cut out therefrom to form an adhesive layer.

Using these two types of sheets as an adhesive layer, an adhesive layer having a higher polyethylene content was placed on a polyethylene plate-shaped sample, and an adhesive layer having a lower polyethylene content was placed thereon, and further, The LCP specimen was placed thereon and heat-sealed in the same manner as in Example 1. Hereinafter, the tensile shear strength was determined in the same manner as in Example 1, and the results are shown in Table 1.

(Example 5) The above-mentioned (A) thermotropic liquid crystal polymer, (B) polyethylene and (D) the resin composition for an adhesive described in Example 3 were extruded in this order in an extruder for a core layer (caliber size). 40mm), extruder for outermost layer (50m diameter)
m), is supplied to an extruder for an adhesive layer (caliber 40 mm), and after being formed into a parison by a co-extrusion blow die (die temperature 330 ° C.), compressed air is drawn into the mold at 0.5 MPa.
The thickness of the layer having the B / C / A / C / B configuration is 1 / 0.2 / 0.2 /
A bottle of 0.2 / 1 mm, 500 ml capacity was molded.

A rectangular specimen having a width of 15 mm was cut out from the side of the bottle, and (A) thermotropic liquid crystal polymer and (D)
The adhesive strength with the resin composition for adhesives was measured. As a result of measuring at a peel angle of 90 ° and a peel speed of 50 mm / min, 82 was obtained.
(N / 15 mm).

The bottle was charged with 150 g of commercial regular gasoline and stored at room temperature for 8 weeks with the metal cap on. As a result, the weight loss due to gasoline pervaporation was 1.2 g.

Comparative Example 1 The ends of the LCP test piece and the polyethylene plate-like test piece in Example 1 were directly overlapped with each other, and were heat-sealed in the same manner as in Example 1. However, it was attempted to determine the tensile shear strength by using this as in Example 1, but it could not be measured due to almost no adhesive strength.

Comparative Example 2 Admer (SF731, manufactured by Mitsui Chemicals, Inc.), which is a copolymer of an unsaturated carboxylic acid and a polyolefin, was hot-pressed at 200 ° C. to a thickness of 0.1%.
mm sheet. This was used as an adhesive layer, and was heat-sealed between the LCP specimen and the polyethylene plate specimen under the same conditions as in Example 1, but the viscosity of the admer was low and it leaked out of the specimen. . Also, with respect to thermotropic liquid crystal polymer and polyethylene, the admer had a clearly lower viscosity, and co-extrusion was not possible.

[0077]

[Table 1]

[0078]

Industrial Applicability The present invention provides an adhesive resin composition having excellent heat resistance, adhesive property and moldability as an adhesive for bonding a thermotropic liquid crystal polymer layer and a polyolefin layer, and a resin for the adhesive. A laminate of a thermotropic liquid crystal polymer layer and a polyolefin layer using the composition and having excellent moldability and barrier properties can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) C09J 167/03 C09J 167/03 177/12 177/12 F term (reference) 4F100 AK01A AK01C AK01G AK03B AK03C AK03G AK04 AK43 AK43C AK43G AK62B AK62C AK62G AK66B AK66C AK66G AL01C AL01G AL04C AS00A BA02 BA03 BA10A BA10B BA15 CB00 GB23 JA06C JA11A JA11C JA11G JD02 JJ03 JJ10A JJ10C JL01 JL11 YY00C 4J029 AA03 AB07 AC01 AC02 AD01 AD07 AE13 BB10A BB10B CB05A CB06A CC05A CC06A CD03 CF08 KB02 4J040 DA021 DA041 DA101 DA111 DA131 DL061 ED041 EG041 LA01 LA06 LA08 LA11 MA10 MA11 MB03

Claims (16)

[Claims] 1. A resin composition for an adhesive comprising (A) a thermotropic liquid crystal polymer and (B) a polyolefin. 2. The resin composition for an adhesive according to claim 1, comprising (A) a thermotropic liquid crystal polymer, (B) a polyolefin, and (C) a polyarylate. 3. The resin for an adhesive according to claim 1, comprising (A) a thermotropic liquid crystal polymer, (B) a polyolefin, and (D) a copolymer of an unsaturated carboxylic acid or a derivative thereof and a polyolefin. Composition. 4. The resin composition for an adhesive according to claim 1, which has a melt viscosity of 100 (Pa · s) or more. 5. The method according to claim 1, wherein (A) the melt viscosity of the thermotropic liquid crystal polymer is 100 (Pa · s) or more.
The resin composition for an adhesive according to any one of the above. 6. The polyolefin (B) having a melt viscosity of 10
The resin composition for an adhesive according to any one of claims 1 to 4, which is 0 (Pa · s) or more. 7. The resin composition for an adhesive according to claim 2, wherein (C) the polyarylate is a polyester having a structure represented by the general formula (1). General formula (1) (Wherein, R represents a hydrogen atom, or a C _m H _{2m + 1} alkyl groups, m is an integer of 1-8) 8. The adhesive for an adhesive according to claim 7, wherein the aromatic dicarboxylic acid component of the general formula (1) in the polyarylate (C) is 5 to 100 mol% of isophthalic acid and 95 to 0 mol% of terephthalic acid. Resin composition. 9. (C) R of the general formula (1) of polyarylate
The resin composition for an adhesive according to claim 7, wherein is a methyl group. 10. The method according to claim 3, wherein the copolymer (D) of the unsaturated carboxylic acid or its derivative and the polyolefin has a graft amount of the unsaturated carboxylic acid or its derivative of 0.01 to 10% by weight. Resin composition for adhesives. 11. The weight ratio of (A) thermotropic liquid crystal polymer to (B) polyolefin is from 10/90 to 90.
The resin composition for an adhesive according to claim 1, which is / 10. 12. The weight ratio of (A) thermotropic liquid crystal polymer to (B) polyolefin is from 10/90 to 90.
/ 10, and the weight ratio of the composition comprising (A) and (B) to (C) polyarylate is from 10/90 to 99 /.
The resin composition for an adhesive according to any one of claims 2 or 4 to 9, which is 1. 13. The weight ratio of (A) thermotropic liquid crystal polymer to (B) polyolefin is from 10/90 to 90.
/ 10, and the weight ratio of the composition comprising (A) and (B) to the copolymer (D) of the unsaturated carboxylic acid or its derivative and the polyolefin is 10/90 to 99/1. Item 11. The resin composition for an adhesive according to any one of Items 3 to 6, or 10. 14. The adhesive composition according to claim 1, wherein (I) a thermotropic liquid crystal polymer layer and (II) a polyolefin layer. The laminate containing as. 15. The content of the thermotropic liquid crystal polymer in the adhesive layer (III-1) in contact with the (I) thermotropic liquid crystal polymer layer is larger than that of the polyolefin, and
The laminate according to claim 14, comprising (II) two or more adhesive layers, wherein the content of the polyolefin in the adhesive layer (III-2) in contact with the polyolefin layer is larger than that of the thermotropic liquid crystal polymer. 16. The laminate according to claim 14, wherein the shape is a film or a sheet.