JP3055851B2 - Resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition having excellent compatibility and transparency and further having excellent mechanical properties.

[0002]

2. Description of the Related Art Conventionally, an ethylene-vinyl alcohol copolymer (hereinafter abbreviated as EVOH) alone is insufficient in flexibility and mechanical properties, particularly in impact resistance. Other thermoplastic polymers such as polyolefins are blended. On the other hand, a thermoplastic polymer such as a polyolefin alone has insufficient gas barrier properties, and EVOH may be blended to improve the gas barrier properties. Also, in order to improve the mechanical properties of EVOH, especially the impact resistance, it is also possible to treat EVOH with a boron compound such as boric acid, borax, trifluoroboron, alkyl or arylborane (JP-B-49-20615).
It is known from U.S. Pat.

[0003]

SUMMARY OF THE INVENTION However, EVO
H and thermoplastic polymers such as polyolefins have low affinity and poor compatibility, so molded products and films made of these blends have significantly reduced mechanical properties and significantly reduced transparency. There is a problem. Various methods have been proposed as methods for improving these problems, but none of these methods are satisfactory, and development of new methods is required. In addition, EVOH treated with a boron compound such as boric acid and blended with a thermoplastic polymer such as polyolefin do not show good compatibility and transparency, as is apparent from Comparative Example 2 described later. Thus, an object of the present invention is to provide excellent compatibility and transparency,
Another object is to provide a resin composition having excellent mechanical properties.

[0004]

An object of the present invention is to provide an EVOH.
(A) and a thermoplastic polymer having at least one functional group selected from the group consisting of a boronic acid group, a borinic acid group, and a boron-containing group that can be converted to a boronic acid group or a borinic acid group in the presence of water (B This is achieved by providing a resin composition comprising: Further, the above object is achieved by providing a resin composition in which a thermoplastic resin (C) other than (A) and (B) is further added to the components (A) and (B).

In the present invention, a resin composition having excellent compatibility and good transparency by blending the above components (A) and (B) and further blending the above component (C). It is surprising that a melt-kneaded resin composition can be obtained. Although the cause is not clear, the above-mentioned functional group of the thermoplastic resin and E
It is presumed that the hydroxyl group of VOH is bonded by transesterification. In the present invention, a resin composition having excellent transparency means that the resin composition of EVOH and an unmodified thermoplastic resin containing no boronic acid group or borinic acid group is superior in transparency to a resin composition. means.

[0006] EVOH used in the present invention is ethylene-
It is a saponified vinyl ester copolymer, and the content of ethylene unit is not particularly limited, but is selected in the range of 10 to 99 mol%, preferably 15 to 60 mol%, and more preferably 20 to 99 mol%.
60 mol% is preferred and optimally 25 to 55 mol%. The saponification degree of the vinyl ester unit of EVOH is selected from the range of 10 to 100 mol%,
It is preferably 00 mol%, more preferably 80 to 100 mol%, most preferably 95 to 100 mol%, and most preferably 99 to 100 mol%. If the degree of saponification is too low, the degree of crystallization may be reduced, or the thermal stability during melt molding may be deteriorated. Therefore, the degree of saponification is preferably higher. Here, as the vinyl ester, vinyl acetate may be mentioned as a representative example, and in addition, vinyl esters such as vinyl propionate, vinyl pivalate, vinyl valerate, vinyl caprate, and vinyl benzoate may also be mentioned. These vinyl esters may be used alone or in combination of two or more. The EVOH may be a mixture of EVOHs different in at least one of the ethylene content, the degree of saponification, and the degree of polymerization. It is important that the EVOH used in the present invention is water-insoluble and thermoplastic.

[0007] EVOH may contain other copolymer components as long as the object of the present invention is not impaired. Here, the other component is an olefin monomer such as propylene, 1-butene, isobutene; an acrylamide monomer such as acrylamide, N-methylacrylamide, N-ethylacrylamide, N, N-dimethylacrylamide; Methacrylamide monomers such as amide, N-methylmethacrylamide, N-ethylmethacrylamide, N, N-dimethylmethacrylamide; methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether, t-butyl vinyl ether And vinyl ether monomers such as dodecyl vinyl ether; allyl alcohol; vinyl trimethoxysilane; N-vinyl-2-pyrrolidone.

The preferred degree of polymerization of the EVOH used in the present invention is 85% by weight of phenol and 15% by weight of water.
The intrinsic viscosity in a mixed solvent of 30 ° C. is preferably 0.1 to 5 desilitters / g (hereinafter abbreviated as dl / g), more preferably 0.2 to 2 dl / g.

The thermoplastic polymer having at least one functional group selected from a boronic acid group, a borinic acid group and a boron-containing group which can be converted to a boronic acid group or a borinic acid group in the presence of water used in the present invention ( B) means that at least one functional group selected from the group consisting of a boronic acid group, a borinic acid group, and a boron-containing group that can be converted to a boronic acid group or a borinic acid group in the presence of water is mainly formed by a boron-carbon bond. It is a thermoplastic polymer attached to a chain, side chain or terminal. Of these, a thermoplastic polymer having the above functional group bonded to a side chain or a terminal is preferable, and a thermoplastic polymer having a terminal bonded thereto is most suitable. Here, the term "end" means one end or both ends. Further, the carbon of the boron-carbon bond is derived from a base polymer of the thermoplastic polymer (B) described later or derived from a boron compound reacted with the base polymer. Preferable examples of the boron-carbon bond include a bond between boron and an alkylene group in a main chain or a terminal or a side chain.

In the present invention, the boronic acid group is represented by the following formula (I).

[0011]

Embedded image

The boron-containing group which can be converted into a boronic acid group in the presence of water (hereinafter simply referred to as boron-containing group) is represented by the above formula (I) after being hydrolyzed in the presence of water. Any boron-containing group that can be converted to a boronic acid group,
Any one may be used, and as typical examples, a boronic ester group represented by the following general formula (II) and a boronic ester group represented by the following general formula (II)
The boronic acid anhydride group represented by I) and the boronic acid salt group represented by the following general formula (IV) are exemplified.

[0013]

Embedded image

[0014]

Embedded image

[0015]

Embedded image

In the formula, X and Y represent a hydrogen atom, an aliphatic hydrocarbon group (such as a linear or branched alkyl group or alkenyl group having 1 to 20 carbon atoms), and an alicyclic hydrocarbon group (cyclo). Alkyl group, cycloalkenyl group, etc.), aromatic hydrocarbon group (phenyl group, biphenyl group, etc.)
X and Y may be the same or different. X and Y may be bonded. However, it is excluded when both X and Y are hydrogen atoms. R ¹ , R ² , and R ³ represent the same hydrogen atom, aliphatic hydrocarbon group, alicyclic hydrocarbon group, and aromatic hydrocarbon group as those of X and Y, and R ¹ , R ² , R 3
³ may be the same or different. M represents an alkali metal or an alkaline earth metal. Further, X, Y, R ¹ , R ² and R ³ may have other groups such as a carboxyl group and a halogen atom. ｝

Specific examples of the boronic ester groups represented by the general formulas (II) to (IV) include boronic acid dimethyl ester group, boronic acid diethyl ester group, boronic acid dipropyl ester group, boronic acid diisopropyl ester group, and boronic acid. Acid dibutyl ester group, boronic acid dihexyl ester group, boronic acid dicyclohexyl group, boronic acid ethylene glycol ester group, boronic acid propylene glycol ester group (boronic acid 1,2-propanediol ester group, boronic acid 1,3-propanediol ester Group),
Boronic acid ester groups such as boronic acid trimethylene glycol ester group, boronic acid neopentyl glycol ester group, boronic acid catechol ester group, boronic acid glycerin ester group, and boronic acid trimethylolethane ester group; boronic acid anhydride group; boronic acid And alkaline earth metal bases of boronic acid.

In the present invention, the borinic acid group is represented by the following formula (V).

[0019]

Embedded image

The boron-containing group capable of being converted to a borinic acid group in the presence of water includes a boron-containing group capable of being converted to a borinic acid group represented by the above formula (V) upon hydrolysis in the presence of water. Any examples are possible, but as typical examples, a borinic acid ester group represented by the following general formula (VI), a borinic anhydride group represented by the following general formula (VII), and a bolinic acid anhydride group represented by the following general formula (VIII) The borinic acid base shown is mentioned.

[0021]

Embedded image

[0022]

Embedded image

[0023]

Embedded image

In the above formulas (V) to (VIII), X has the same meaning as X in the above formula (II), and Z is the same aliphatic hydrocarbon group or alicyclic hydrocarbon as X described above. Group, aromatic hydrocarbon group, amino group, and amide group. X and Z may be bonded. R ¹ , R ² , and R ³ are represented by the general formula (I
It has the same meaning as R ¹ , R ² and R ^{3 in} V). M has the same meaning as M in the general formula (IV). ｝

Specific examples of the bolinic acid ester groups represented by the general formulas (V) to (VIII) include X, Z, R ¹ , R ² and R ³
Represents a lower hydrocarbon group such as a methyl group, an ethyl group, a propyl group, a butyl group, a 1-methylpropyl group, a pentyl group, a hexyl group, and a phenyl group. Representative examples include a methyl borinic acid group, a methyl borinic acid methyl ester group, an ethyl borinic acid methyl ester group, a methyl borinic acid ethyl ester group, a butyl borinic acid methyl ester group, and a 3-methyl-2-butyl borinic acid methyl ester group. Among these functional groups, a boronic acid ester group such as a boronic acid ethylene glycol ester group is particularly preferred from the viewpoint of compatibility with EVOH (A). The above-mentioned boron-containing group which can be converted into a boronic acid group or a borinic acid group in the presence of water means the thermoplastic polymer (B) as water or water and an organic solvent (toluene, xylene, acetone, etc.)
In a mixed liquid of a boric acid aqueous solution and the organic solvent, a reaction time of 10 minutes to 2 hours, and a reaction temperature of room temperature to 1 hour.
It means a group that can be converted into a boronic acid group or a borinic acid group when hydrolyzed at 50 ° C.

The content of the functional group is not particularly limited.
It is preferably 0.0001 to 1 meq / g (milli-equivalent / g), and particularly preferably 0.001 to 0.1 meq / g.
It is surprising that the compatibility, transparency and the like of the resin composition are remarkably improved by the presence of such a small amount of the functional group.

Representative examples of the base polymer of the thermoplastic polymer (B) include olefin polymers, vinyl polymers and diene polymers which are essentially incompatible with EVOH. As monomers constituting the olefin-based polymer, vinyl-based polymer, and diene-based polymer, α-olefins such as ethylene, propylene, 1-butene, isobutene, 3-methylpentene, 1-hexene, and 1-octene Monomers such as vinyl acetate, vinyl propionate and vinyl pivalate; methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate;
Acrylate monomers such as octyl acrylate, dodecyl acrylate and 2-ethylhexyl acrylate; methyl methacrylate, ethyl methacrylate,
Methacrylic acid ester monomers such as butyl methacrylate, octyl methacrylate, dodecyl methacrylate; acrylamide, N-methylacrylamide, N-
Acrylamide monomers such as ethyl acrylamide and N, N-dimethylacrylamide; methacrylamide, N
Methacrylamide monomers such as -methylmethacrylamide, N-ethylmethacrylamide, N, N-dimethylmethacrylamide; vinyl halide monomers such as vinyl chloride, vinylidene chloride and vinyl fluoride; styrene, α-
Aromatic vinyl monomers such as methylstyrene; acrylonitrile monomers such as acrylonitrile and methacrylonitrile; and diene monomers such as butadiene and isoprene.

The base polymer is used as a polymer composed of one, two or three or more of these monomers. Among these base polymers, especially ethylene-based polymer ｛ultra low density polyethylene, low density polyethylene,
Medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer, metal salt of ethylene-acrylic acid copolymer (Na, K, Zn ionomer) ), Ethylene-propylene copolymers, etc., propylene polymers, aromatic vinyl polymers (polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-butadiene-acrylonitrile copolymer, styrene- Maleic anhydride copolymer), diene polymer {aromatic vinyl monomer-diene monomer-
Block copolymer hydrogenated aromatic vinyl monomer, polyisoprene, polybutadiene, chloroprene, isoprene-acrylonitrile copolymer (nitrile rubber), isoprene-isobutene copolymer (butyl rubber), etc. No.

The preferred melt index (MI) of the thermoplastic polymer (B) used in the present invention (190 ° C., 216
(Value measured under a load of 0 g) is 0.01 to 1000 g / 1.
0 minutes is preferable, and 0.1 to 100 g / 10 minutes is more preferable.

Next, a typical method for producing a thermoplastic polymer (B) having at least one functional group of a boronic acid group, a borinic acid group and a boron-containing group used in the present invention will be described. First production method: An olefin polymer having a boronic acid group, a borinic acid group, or a boron-containing group at a terminal is obtained by thermally decomposing the olefin polymer, introducing a double bond mainly at a terminal, and then adding a borane complex to the olefin polymer. And a trialkyl borate.

The starting olefin polymer is ethylene,
MI (230 ° C., 2160 g) composed of olefin monomer units such as propylene and 1-butene is 10 g / 10
Minutes or less, more preferably an olefin polymer having a high degree of polymerization of 1 g / 10 minutes or less.

The thermal decomposition is carried out under an oxygen-free condition such as a nitrogen atmosphere or a vacuum, and the reaction temperature is from 300 ° C. to 500 ° C.
C. and the reaction time is preferably 1 minute to 10 hours. The degree of thermal decomposition is preferably such that the amount of double bonds in the olefin polymer produced by thermal decomposition is in the range of 0.001 to 0.2 meq / g.

The introduction of the boronic acid group is carried out by heating and reacting an olefin polymer having a double bond, a borane complex, a trialkyl borate and a solvent of these three components with stirring under a nitrogen atmosphere. It is.
As the borane complex, a borane-tetrahydrofuran complex, a borane-dimethylsulfide complex, a borane-pyridine complex, a borane-trimethylamine complex, a borane-triethylamine complex, and the like are preferable. Among these, a borane-triethylamine complex and a borane-trimethylamine complex are more preferred. The amount of the borane complex charged is from 1/3 equivalent to 10 equivalents to the double bond of the olefin polymer.
The equivalent range is preferred. As the trialkyl borate, lower alkyl borate esters such as trimethyl borate, triethyl borate, tripropyl borate and tributyl borate are preferable. The amount of trialkyl borate to be charged is preferably in the range of 1 to 100 equivalents based on the double bond of the olefin polymer. The solvent does not need to be particularly used, but when used, a saturated hydrocarbon solvent such as hexane, heptane, octane, decane, dodecane, cyclohexane, ethylcyclohexane, and decalin is preferable.

The reaction for introducing a boronic acid group into an olefin polymer having a double bond is performed at a reaction temperature of room temperature to 300 ° C.
The reaction is preferably carried out at 100 to 250 ° C. and for a reaction time of 1 minute to 10 hours, preferably 5 minutes to 5 hours. The type of boronic acid group or boron containing group can be easily interconverted by the presence of water or alcohol. For example, boronic acid dimethyl ester becomes boronic acid by reacting with water, and boronic acid becomes ethylene glycol ester by reacting with ethylene glycol. The type of this ester group affects the melt index. In general, a melt index is increased by reacting a polyolefin having a boronic acid group with a diol such as ethylene glycol or 1,3-propanediol to form a cyclic ester. Therefore, the melt index can be adjusted by increasing or decreasing the amount of the ester group.

A second process for producing the thermoplastic polymer (B); an olefin polymer or a vinyl polymer having at least one functional group selected from a boronic acid group, a borinic acid group and a boron-containing group at the terminal; The diene polymer radically polymerizes at least one selected from olefin monomers, vinyl monomers, and diene monomers in the presence of a thiol having a boronic acid group, a borinic acid group, or a boron-containing group. Obtained by:

The thiol having a boronic acid group or a boron-containing group as a raw material can be obtained by reacting a thiol having a double bond with a diborane or a borane complex in a nitrogen atmosphere and then adding an alcohol or water. Also. The thiol having a borinic acid group or a boron-containing group can be obtained by reacting a thiol having a double bond, a diborane or a borane complex and an olefin under a nitrogen atmosphere, and then adding an alcohol or water. Here, as the thiol having a double bond, 2-propen-1-thiol, 2-methyl-2-propen-1-thiol, 3
-Butene-1-thiol, 4-pentene-1-thiol and the like, among which 2-propen-1-thiol and 2-methyl-2-propen-1-thiol are preferred. As the borane complex, those similar to those described above are used, and among them, a borane-tetrahydrofuran complex is particularly preferable. The amount of diborane or borane complex to be added is preferably approximately equivalent to thiol having a double bond. The reaction conditions are preferably from room temperature to 200 ° C. Examples of the solvent include ether solvents such as tetrahydrofuran (THF) and diglyme; and saturated hydrocarbon solvents such as hexane, heptane, ethylcyclohexane, and decalin. Of these, THF is preferable. As alcohols added after the reaction, lower alcohols such as methanol and ethanol are preferable, and methanol is particularly preferable. The olefins to be added when producing the thiol having a borinic acid group are not particularly limited, but ethylene, propylene, 1-butene, 2-butene, 1-pentene, 2-pentene, 2-methyl-1- Lower olefins such as butene, 2-methyl-2-butene, 1-hexene and cyclohexene are preferred.

In the presence of a thiol having at least one functional group selected from a boronic acid group, a borinic acid group and a boron-containing group, an olefin monomer, a vinyl monomer, a diene By subjecting at least one selected from the system monomers to radical polymerization, a polymer having the functional group at the terminal can be obtained. As the polymerization conditions,
An azo- or peroxide-based initiator is used, and the polymerization temperature is preferably in the range of room temperature to 150 ° C. The amount of the thiol having a functional group is 0.001 per gram of the monomer.
The amount of the thiol is preferably about 1 mmol, and the method of adding the thiol is not particularly limited. However, when a monomer such as vinyl acetate or styrene which is easily chain-transferred is used, the thiol may be fed during the polymerization. Preferably, when using a substance such as methyl methacrylate, which hardly undergoes chain transfer, thiol is preferably added from the beginning.

The third method for producing the thermoplastic polymer (B); the thermoplastic resin having at least one functional group selected from a boronic acid group, a borinic acid group and a boron-containing group in a side chain includes a boronic acid group, A monomer having at least one functional group selected from an acid group and a boron-containing group and at least one monomer selected from the olefin-based monomers, vinyl monomers, and diene-based monomers described above. It is obtained by polymerizing. Here, the monomer having at least one functional group selected from a boronic acid group, a borinic acid group and a boron-containing group includes, for example, 3-acryloylaminobenzeneboronic acid, 3-methacryloylaminobenzeneboronic acid, 4-vinyl Benzeneboronic acid and the like. Further, a thermoplastic polymer having at least one functional group selected from a boronic acid group, a borinic acid group, and a boron-containing group in a side chain includes, for example, acrylic acid, methacrylic acid, itaconic acid, citraconic acid, fumaric acid, and anhydride. The carboxyl group of a copolymer or graft copolymer of an unsaturated carboxylic acid such as maleic acid and at least one of the olefin-based monomers, vinyl-based monomers, and diene-based monomers described above is used as a carbodiimide. It can also be obtained by performing an amide reaction with an amino group-containing boronic acid such as m-aminobenzeneboronic acid, with or without the use of a condensing agent.

The resin composition of the present invention comprises the above-described EVOH
(A) and a thermoplastic polymer (B) having at least one functional group selected from a boronic acid group, a borinic acid group and a boron-containing group, and the weight ratio of the component (A) to the component (B) is as follows: 99: 1 to 1:99, 9
5: 5 to 5:99 are more preferred. When heat resistance and mechanical properties are imparted to the component (A), (A) :( B) is 9
The ratio is preferably 5: 5 to 50:50, and the component (B)
(A) :( B) is preferably from 5:95 to 50:50 when imparting gas barrier properties and solvent resistance to the rubber. When an olefin polymer, especially a propylene polymer is used as the base polymer of the component (B),
As is clear from Examples 1 and 2 described below, the hot water resistance is improved, and therefore, it is extremely useful as a field requiring hot water resistance, for example, as a packaging material for retorts. Examples of the base polymer of the component (B) include an ethylene polymer, a diene polymer, an aromatic vinyl monomer (such as styrene), a diene monomer (such as isoprene and butadiene), and an aromatic vinyl monomer. When｝ such as a block copolymer hydrogenated product is used, as is apparent from Examples 3 to 6 described below,
Since the impact resistance is improved, it is useful as a packaging material for fields requiring impact resistance, such as bottles, tubes, cups, and pouches.

Further, the resin composition of the present invention comprises the component (A)
And a thermoplastic polymer (C) other than the component (A) and the component (B), particularly the component (A).
A mode in which a thermoplastic polymer (C) which is essentially incompatible with water is also included. In the present invention, even when a thermoplastic polymer (C) having essentially no compatibility with the component (A) is blended, a resin composition having excellent compatibility and transparency can be obtained due to the presence of the component (B). This is surprising, and is shown in Example 2 below. In this case, the weight ratio of the components (A), (B) and (C) is
(A): [(B) + (C)] is selected from the range of 99: 1 to 1:99, and more preferably 95: 5 to 5:95. When hot water resistance and mechanical properties are imparted to the component (A), (A): [(B) + (C)] is 95: 5 to 50: 5.
0 is preferable, and when imparting gas barrier properties and solvent resistance to the components (B) and (C), (A):
[(B) + (C)] is preferably from 5:95 to 50:50. For example, when the base polymer of the component (B) and the (C) are propylene-based polymers, if the purpose is to improve the gas barrier properties and solvent resistance of the propylene-based polymer, then (A): [(B) + (C)] is 5: 95-4
The range of 5:55 is preferred, and for the purpose of imparting hot water resistance to the EVOH (A), (A): [(B) + (C)]
Is preferably in the range of 95: 5 to 55:45. Examples of the resin (C) used here include a base polymer of the component (B), particularly a base polymer that is essentially incompatible with EVOH, and one or more of these base polymers may be used. used. Further, as the resin (C), polyester (polyethylene terephthalate, polybutylene phthalate, etc.), polyamide, polycarbonate, polyvinylidene chloride, polyvinyl chloride, polyurethane, polyacetal and the like can also be used. Known methods such as a blending method using a Banbury mixer and a melt blending method using a single-screw or twin-screw extruder can be adopted as a method for blending these components. At that time, blending can be performed by a master batch method. In addition, other additives such as an antioxidant, an ultraviolet absorber, a lubricant, a plasticizer, an antistatic agent, a colorant, and a heat stabilizer are not limited to the extent that the effects of the present invention are not impaired. , Alkali metal acetates, alkaline earth metal acetates, higher fatty acid salts (calcium stearate, sodium stearate, etc.), phosphorus compounds (calcium phosphate, potassium phosphate, magnesium phosphate, sodium phosphate, etc.), inorganic substances (for example, Mica, montmarillonite, talc, sericite, glass fiber, bentonite, clay, hydrotalcite, metal oxide, metal hydroxide, metal salt) and the like.

The resin composition of the present invention can be easily molded by a known melt molding method (T-die extrusion, inflation extrusion, blow molding, injection molding, press molding).
Film, sheet, cup, tube, bottle, fiber,
It can be molded into any molded article such as a rod or a tube. The dispersed particle size of the island component (A) or (B) or the mixture of (B) and (C) in the obtained molded product is small, and is 0.01%.
２2 μm, preferably 0.01-1 μm.

The resin composition of the present invention may be a multilayer structure having an EVOH layer and a thermoplastic resin (polyolefin or the like) layer, for example, a multilayer structure composed of an EVOH layer / thermoplastic resin layer, a thermoplastic resin layer / A mode in which the component (B) used in the present invention is blended and used in a scrap generated when a film, a sheet, a tube, a bottle, or the like is manufactured from a multilayer structure composed of an EVOH layer / a thermoplastic resin layer is also included. Further, the resin composition of the present invention, other thermoplastic resin,
For example, it is suitably used as a base polymer of the above-mentioned component (B), and further as a multilayer structure of polyester (polyethylene terephthalate, polybutylene terephthalate, etc.), polyamide, polycarbonate, polyvinyl chloride, polyvinylidene chloride, polyurethane, polyacetal, EVOH and the like. Used. The multilayer structure is formed by a known method such as co-extrusion, co-injection, or extrusion coating, and the scrap of these molded products can be reused. When the scrap is reused, the resin composition of the present invention is used. Can be compounded in the scrap, or the component (B) used in the present invention can be compounded in the scrap. A container such as a cup can be obtained by thermoforming a multilayer structure, particularly a multilayer sheet or a multilayer film, or a desired tube can be obtained by blow molding or biaxial stretching blow molding a multilayer structure, particularly a parison. , Can be a bottle.

In the case of obtaining a multilayer structure, it is often preferable to interpose an adhesive resin layer between the resin composition layer of the present invention and the thermoplastic resin layer because both layers can be firmly bonded. Here, the adhesive resin is not particularly limited as long as it strongly adheres both layers, but the unsaturated carboxylic acid or its anhydride (maleic anhydride or the like) may be an olefin polymer or a copolymer. Polymers [Polyethylene @ low density polyethylene, linear low density polyethylene (LLDPE), ultra low density polyethylene (SLDP)
E)｝, ethylene-vinyl acetate copolymer, ethylene-
(Meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester (methyl ester or ethyl ester) copolymer, polypropylene, etc.), and hydrogenated styrene-butadiene copolymer acid anhydride (anhydrous Modified products of maleic acid and the like, modified acid anhydrides of liquid polybutadiene, modified acid anhydrides of diene polymers such as modified acid anhydrides of ethylene-propylene-diene copolymer, and the like are preferably used.

The layer structure of the multilayer structure is as follows: resin composition layer / thermoplastic resin layer, resin composition layer / thermoplastic resin layer /
Resin composition layer, thermoplastic resin layer / resin composition layer / thermoplastic resin layer, thermoplastic resin layer / resin composition layer / scrap collecting layer / thermoplastic resin layer, thermoplastic resin layer / scrap collecting layer / resin composition Material layer / scrap recovery layer / thermoplastic resin layer, or those in which the above-mentioned adhesive resin layer is interposed between at least one of these layers.

Molded articles and multilayer structures obtained from the above-described resin composition of the present invention can be used for foods requiring gas barrier properties,
It is particularly useful as a packaging material for pharmaceuticals, medical equipment, clothing, and the like. Fuels that require impact resistance (such as gasoline)
It is useful as a tube tank or a pesticide bottle.

[0046]

The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the invention thereto. In the following Synthesis Examples and Examples, unless otherwise specified, the ratio means the weight ratio, and “%” means “% by weight”. The melt index (hereinafter abbreviated as MI) was measured at 190 ° C. under a load of 2160 unless otherwise noted.
It is a value measured in g. The limiting viscosity is phenol 85
It is measured at 30 ° C. in a mixed solvent of 15% by weight of water and 15% by weight of water (hereinafter abbreviated as hydrous phenol). The amount of double bonds in the polyolefin was determined by 270 MHz ¹ H-NMR using heavy para-xylene as a solvent. The amounts of boronic acid groups and their ester groups in polypropylene and polyethylene were determined by using a mixed solution of heavy para-xylene: chloroform: ethylene glycol = 8: 2: 0.02 as a solvent at 270 MHz ¹ H-NMR.
And the amount of boronic acid groups in the other resin was determined by using chloroform: ethylene glycol = 10: 0.
270 MHz ¹ using a mixed solution having a ratio of 02 as a solvent.
It was quantified by 1 H-NMR. The amount of borinic acid and its ester group was determined by using deuterated chloroform as a solvent at 500 MH.
It was quantified by z ¹ H-NMR. Haze measurement method is JI
Performed by SK7105.

Synthesis Example 1 Synthesis of Polypropylene Having a Double Bond at the Terminal: A separable flask was charged with 200 g of polypropylene {MI (230 ° C., load 2160 g), 0.3 g / 10 min}, and a bath temperature of 250 ° C. under vacuum. After heating for 1 hour, the bath temperature was further raised to 340 ° C., and then heating was performed for 2 hours. After cooling, the polypropylene was taken out and pulverized to obtain a polypropylene having a double bond amount of 0.031 meq / g and MI having a double bond at a terminal of 80 g / 10 min.

Synthesis Example 2 Synthesis of polypropylene having a boronic acid group at its terminal: 100 g of the polypropylene obtained in Synthesis Example 1 and 200 g of decalin were placed in a separable flask equipped with a condenser and a stirrer, and after purging with nitrogen, ° C, and nitrogen was further introduced into the reactor for 30 minutes. 5.5 g of trimethyl borate and borane-triethylamine complex 76
After adding 0 milligram (mg) and performing a reaction at 180 ° C. for 4 hours, the mixture was cooled to room temperature. The obtained gel-like polypropylene is washed well with a 1/1 mixed solution of methanol and acetone, and then dried to obtain a boronic acid group content of 0.025.
Polypropylene (the following formula (IX)) having a meq / g and MI of 4 g / 10 minutes was obtained.

[0049]

Embedded image

270 MHz ¹ HN of the obtained polymer
The MR chart is shown in FIG. 1, where the peak at 3.8 ppm indicates the presence of boronic acid ethylene glycol ester formed by reacting boronic acid in the polymer with ethylene glycol in the solvent.

Synthesis Example 3 Synthesis of ethylene-propylene copolymer having a double bond at a terminal: A propylene content of 26% was placed in a separable flask.
MI (230 ° C., load 2160 g) 250 g of an ethylene-propylene copolymer 0.7 g / 10 min was charged, and heated at a bath temperature of 280 ° C. for 30 minutes under vacuum.
By heating to 0 ° C. and heating for 2 hours and 10 minutes, the propylene content was 26% and the amount of double bonds was 0.035 meq /
g, MI 8 g / 10 minutes to obtain an ethylene-propylene copolymer having a double bond at the terminal.

Synthesis Example 4 Synthesis of ethylene-propylene copolymer having a boronic acid terminal: Synthesis Example 3 in a separable flask equipped with a condenser
30 g of the ethylene-propylene copolymer obtained in the above, 145 mg of a borane-pyridine complex, and tributyl borate 1.1
2 g were charged and the atmosphere was replaced with nitrogen. After performing the reaction at 170 ° C. for 40 minutes, the temperature was raised to 220 ° C., and the reaction was performed for 1 hour. After cooling to room temperature, the obtained gel polymer was dissolved in toluene, reprecipitated with a mixed solvent of methanol-acetone 1: 1, and purified by repeating the above. By vacuum drying at 80 ° C. for 12 hours, an ethylene-propylene copolymer having a boronic acid group content of 0.018 meq / g and an MI of 1.5 g / 10 minutes was obtained.

Synthesis Example 5 Synthesis of low-density polyethylene having a double bond at the end: 200 g of low-density polyethylene having an MI of 0.35 g / 10 minutes was charged into a separable flask, and the bath temperature was 260 ° C. under vacuum.
After heating at 340 ° C. for 30 minutes and heating for 2 hours, the amount of double bonds is 0.06 meq.
/ G, MI 90 g / 10 min to obtain a low density polyethylene having a double bond.

Synthesis Example 6 Synthesis of low density polyethylene having a boronic acid group at the terminal:
30 g of the low-density polyethylene obtained in Synthesis Example 5 and borane-pyridine complex 30 in a separable flask equipped with a condenser
0 mg, tributyl borate 2.25 g, decalin 50 g
, And the mixture was reacted at 190 ° C. for 3 hours after purging with nitrogen. After cooling to room temperature, the resulting gel-like polyethylene was thoroughly washed with a mixed solvent of methanol-acetone 1: 1 and then dried to obtain a boronic acid group content of 0.035 meq / g,
An ethylene-propylene copolymer having an MI of 2 g / 10 minutes was obtained.

Synthesis Example 7 Synthesis of ethylene glycol ester of 3-mercaptopropylboronic acid: A flask equipped with a condenser and a dropping funnel was charged with 19.26 g of sodium borohydride (NaBH ₄ ) and purged with nitrogen. 500 ml of THF dried and distilled with benzophenone and metallic sodium was added thereto, and cooled to 0 ° C. in an ice bath, and then, while stirring, 99.9% of boron trifluoride-diethyl ether complex.
5 g was dropped over 30 minutes. After 2 hours at 0 ° C 2
-45.61 g of propene-1-thiol was added dropwise over 30 minutes. After stirring for 40 minutes, the temperature was raised to 60 ° C., and the mixture was further stirred for 3 hours. After cooling to 0 ° C., 100 ml of methanol was added dropwise over 40 minutes. After the reaction solution was filtered to remove solids, the solvent was distilled off, 38 g of ethylene glycol was added, and the mixture was extracted with methylene chloride-water to remove excess ethylene glycol, dried over magnesium sulfate, and dried under reduced pressure to give 3-mercapto. 4: 1 mixture 4 of ethylene glycol boronate and ethylene glycol 2-mercapto-1-methylethylboronate
6.7 g was obtained {boiling point 70 ° C. (4 mmHg)}.

Synthesis Example 8 Synthesis of ethylene glycol 4- (2-mercaptoethyl) phenylboronic acid: 2.92 g of 4-vinylphenylboronic acid, 1.38 g of ethylene glycol, and 50 ml of benzene were charged into a flask equipped with a dehydration fractionating tube. , 80
The mixture was heated at 30 ° C. for 30 minutes to remove distilled water. 3.18 g of thioacetic acid and 47 mg of 2,2'-azobisisobutyronitrile were added to this reaction solution, and heated at 75 ° C for 2 hours.
After the reaction solvent was distilled off, the residue was extracted with a methylene chloride / aqueous sodium hydrogen carbonate solution. The methylene chloride layer was dried over magnesium sulfate, and the solvent was distilled off. 5 g of the crude ethylene glycol ester of 4- (2-acetylthioethyl) phenylboronic acid thus obtained, 20 ml of methanol and 10 ml of triethylamine were charged into a flask, reacted at 65 ° C. under nitrogen for 20 hours, and distilled under reduced pressure.
3.55 g of-(2-mercaptoethyl) phenylboronic acid ethyl glycol ester was obtained. ｛Boiling point 135 ° C
(0.2 mmHg)｝.

Synthesis Example 9 Synthesis of methyl 3-mercaptopropyl (3-methyl-2-butyl) borinate: A flask equipped with a dropping funnel and a stirrer was replaced with nitrogen, and 310 ml of a 1N borane THF solution was charged. After cooling to 0 ° C. in an ice bath, 2-methyl-2-butene 21.
74 g was added dropwise over 6 minutes. 30 minutes later at 0 ° C 2
-Propene-1-thiol (22.79 g) was added dropwise over 30 minutes. After stirring for 40 minutes, the temperature was raised to 60 ° C., and the mixture was further stirred for 1 hour. After cooling to 0 ° C., 50 ml of methanol was added dropwise over 12 minutes. After distilling off the solvent, 27.2 g of 3-mercaptopropyl (3-methyl-2-butyl) borinic acid methyl ester was obtained by distillation.
Obtained {boiling point 50 ° C. (0.5 mmHg)}.

Synthesis Example 10 Synthesis of polystyrene having a boronic ester group at the end: 500 g of styrene and ethylene glycol ester of 3-mercaptopropylboronic acid (MPB) obtained in Synthesis Example 7 were placed in a flask equipped with a stirrer and a reflux condenser.
E) 0.0765 g was charged and degassed under reduced pressure. 1
After heating to 20 ° C., a styrene solution containing 0.394% of MPBE and 0.069% of azobiscyclohexanecarbonitrile was fed first at a rate of 7.2 ml, and then fed at a rate of 0.5 ml / min. Stopped. At this time, the polymerization rate was 45%. The polystyrene was purified by reprecipitation with methanol, and further dried to give a boronic acid ethylene glycol ester group at a terminal of 0.013 m 2 MI / 10 min.
A polystyrene having eq / g was obtained.

Synthesis Example 11 Synthesis of polymethyl methacrylate having a boronic acid ethylene glycol ester group at a terminal: 150 g of methyl methacrylate in a flask equipped with a stirrer and a cooler, ethylene glycol 3-mercaptopropyl boronate obtained in Synthesis Example 7 0.876 g of the ester was charged, and degassing was performed by blowing nitrogen. Then, the temperature was raised to 80 ° C., and 0.2 g of separately prepared azobisisobutyronitrile was prepared.
After 1.5 ml of a 3% toluene solution was first added, 0.5 ml was added every 30 minutes. After 5 hours, the mixture was cooled to stop the polymerization. At this time, the polymerization rate was 47%. The resulting polymethyl methacrylate was reprecipitated with methanol and dried to give a boronic acid ethylene glycol ester group at the end of 0.03 meq / min at an MI of 0.5 g / 10 min.
g of polymethyl acrylate (a mixture of the following formula (X) and the following formula (XI) of about 8: 2) was obtained.

[0060]

Embedded image

[0061]

Embedded image

270 MHz ¹ HN of the obtained polymer
An MR chart is shown. The peak at 4.18 ppm indicates the presence of the boronic acid ethylene glycol ester of the formula (X), and the peak at 4.2 ppm indicates the presence of the boronic acid ethylene glycol ester of the formula (XI). Show.

Synthesis Example 12 Synthesis of polymethyl methacrylate having a boronic ester group at the terminal: Synthesis Example 8 in place of ethylene glycol 3-mercaptopropylboronic acid ester of Synthesis Example 11
Polymerization and post-treatment were carried out under the same conditions as in Synthesis Example 11 using 1.248 g of ethylene glycol mercaptoethylphenylboronic acid obtained in the above. As a result, MI 0.5
g / 10 minutes, polymethyl methacrylate having a boronic acid ethylene glycol ester group at a terminal of 0.03 meq / g was obtained.

Synthesis Example 13 Synthesis of polymethyl methacrylate having a borinic acid group at the end: 150 g of methyl methacrylate was placed in a flask equipped with a stirrer and a condenser, and 3-mercaptopropyl (3-methyl-2-methyl) obtained in Synthesis Example 9 was used. Butyl) borinic acid methyl ester was charged and degassed by blowing nitrogen. The temperature was raised to 80 ° C., and a 0.23% toluene solution of azobisisobutyronitrile separately prepared was first added. 0.5 ml every 30 minutes after adding 0.5 ml
Was added. After 5 hours, the mixture was cooled to stop the polymerization. At this time, the polymerization rate was 61%. The resulting polymethyl methacrylate was reprecipitated with methanol and then dried to give a MI having a borinic acid group of 0.5 g / 10 min.
Polymethyl methacrylate having 03 meq / g was obtained.

Synthesis Example 14 Synthesis of hydrogenated styrene-isoprene-styrene block copolymer having a boronic ester group in the side chain: maleic anhydride modified by a known method in a separable flask having a stirrer and a cooler Hydrogenated styrene-isoprene-styrene block copolymer (styrene content 3
5%, hydrogenation rate 96%, maleic anhydride amount 0.03 meq
/ G) 30 g of xylene and 100 g of xylene were charged into a separable flask, and separately, 20 g of xylene, 310 mg of 3-aminophenylboronic acid-hydrate, and 120 mg of ethylene glycol were dehydrated and distilled to prepare 3-aminophenylboronic acid ethylene. A glycol ester / xylene solution was added and heated at 140 ° C. for 3 hours.
After cooling, the precipitate was purified by reprecipitation with methanol containing 0.1% ethylene glycol, and then dried to obtain an MI of 2 g / l.
At 0 minutes, a hydrogenated styrene-isoprene-styrene block copolymer having a boronic acid ethylene glycol ester group in the side chain of 0.028 meq / g was obtained.

Example 1 Polypropylene 5 having a boronic acid group at the terminal of Synthesis Example 2
and EVAL (registered trademark) -F101 manufactured by Kuraray (EVO having an ethylene content of 32 mol%, a saponification degree of 99.5%, and an intrinsic viscosity of 1.1 dl / g at 30 ° C. in hydrous phenol).
H) Using 45 g, melt kneading was performed under the following conditions. Machine used: Plastograph Rotor shape: Roller type Number of revolutions: 80 rpm Kneading temperature: 220 ° C. Kneading time: 10 minutes The resin composition obtained by the above method was hot pressed at 220 ° C. to form a 100 μm thick film. did. This film is broken in liquid nitrogen, and the fracture surface is 1
After extraction with xylene at 40 ° C., the fracture surface was observed with a scanning electron microscope. As a result, the average dispersed particle size of the polypropylene was 0.3 μm, and the haze of this press film was 15%. This piece of film is pressed under pressure for 110 minutes.
When treated with hot water of 30 ° C. for 30 minutes, the shape of the film was hardly deformed.

Comparative Example 1 A film was obtained in the same manner as in Example 1 except that 5 g of unmodified polypropylene (MI 4 g / 10 min) was used instead of 5 g of a polypropylene having a boronic acid group at the terminal. The average dispersed particle size of the unmodified polypropylene is 5 μm, the haze of the film is 43%,
Both transparency were poor. Partially deformed by hot water treatment at 110 ° C.

Comparative Example 2 In place of 5 g of a polypropylene having a boronic acid group at the end, 5 g of unmodified polypropylene (MI 4 g / 10 min) was used, and a boric acid-treated ethylene content of 32 mol% was used as an ethylene-vinyl alcohol polymer. Ethylene-vinyl alcohol copolymer (boric acid content 0.14%, intrinsic viscosity in water-containing phenol at 30 ° C. 0.83 dl / g)
A film was obtained in the same manner as in Example 1 except that the average dispersion particle size of polypropylene in the film was 5
μm, the haze of the film was 40%, and both the compatibility and the transparency were poor. Partially deformed by hot water treatment at 110 ° C.

Comparative Example 3 EVAL (registered trademark) -F101 manufactured by Kuraray Co., Ltd.
After hot pressing at 0 ° C., a hot water treatment was carried out under the same conditions as in Example 1. As a result, the material was completely denatured and could not remain in its original form.

Example 2 Polypropylene 5 having a boronic acid group at the terminal of Synthesis Example 2
g, unmodified polypropylene (MI 1.5 g) 40 g, Kuraray EVAL (registered trademark) -E105 (ethylene content 44 mol%, saponification degree 99.5%, 3 in water-containing phenol)
Using 5 g of intrinsic viscosity (0.96 dl / g) at 0 ° C., melt kneading was performed under the following conditions. Machine used: Plastograph Rotor shape: Roller type Number of revolutions: 80 rpm Kneading temperature: 220 ° C. Kneading time: 10 minutes The resin composition obtained by the above method was hot pressed at 220 ° C. to form a 100 μm thick film. did. This film was broken in liquid nitrogen, and the fracture surface was 8
After extraction with dimethyl sulfoxide (DMSO) at 0 ° C., the fracture surface was observed with a scanning electron microscope. As a result, the average dispersed particle size of the ethylene-vinyl alcohol copolymer in the film was 0.3 μm, and the haze of this press film was 13%.

Comparative Example 4 A film was obtained in the same manner as in Example 2 except that 5 g of polypropylene (MI 4 g / 10 min) was used instead of 5 g of polypropylene having a terminal boronic acid group. The average dispersed particle size of the alcohol copolymer was 6 μm, and the haze was 40%.

Example 3 A film was prepared in the same manner as in Example 1 except that 5 g of an ethylene-propylene copolymer having a boronic acid group at the terminal was used instead of polypropylene having a boronic acid group at the terminal. As a result, the average dispersed particle size of the ethylene-propylene copolymer in the film was 0.4 μm, and the haze of the film was 40%. Further, the notched Izod impact strength of a sample piece obtained by molding the above composition using a small injection molding machine was measured according to the method of JIS K7120, and was found to be 25 kgf · cm / cm ² .

Example 4 In place of polypropylene having a terminal boronic acid group, 10 g of an ethylene-propylene copolymer having a terminal boronic acid group of Synthesis Example 4 was used instead of polypropylene, and EVAL®-F101 manufactured by Kuraray Co., Ltd. (Ethylene content 32 mol%, saponification degree 99.6 mol%, intrinsic viscosity in water-containing phenol at 30 ° C. 1.1 dl / g) Except that 45 g of Eval (registered trademark) was used instead of 45 g, When a film was obtained in the same manner, the average dispersed particle size of the ethylene-propylene copolymer in the film was 0.4 μm, and the haze of the film was 65%. Further, a notched Izod of a sample piece obtained by molding the above composition by a small injection molding machine is used.
When the impact strength was measured according to the method of JIS K7120, it was not broken.

Comparative Example 5 The procedure of Example 4 was repeated except that 10 g of an ethylene-propylene copolymer (propylene content 26%, MI 2 g / 10 min) was used in place of 5 g of an ethylene-propylene copolymer having a boronic acid group at the terminal. When a film was obtained in the same manner, the average dispersion particle size of the ethylene-propylene copolymer in the film was 7 μm, the haze of the film was 83%, and the notched Izod impact strength of the injection-molded sample piece was 9K.
gf · cm / cm ² .

Example 5 A film was prepared in the same manner as in Example 3 except that 5 g of the low-density polyethylene having a boronic acid group of Synthesis Example 6 was used instead of 5 g of the ethylene-propylene copolymer having a boronic acid group at the terminal. As a result, the average dispersed particle size of polyethylene in the film was 0.4 μm, the haze of the film was 12%, and the notched Izod impact strength of the injection-molded sample piece was 12 kgf · cm / cm ² .

Comparative Example 6 Instead of 5 g of an ethylene-propylene copolymer having a boronic acid group at the terminal, low-density polyethylene (MI 2 g / 10
A film was obtained in the same manner as in Example 3 except that 5 g was used. The average dispersed particle size of the polyethylene in the film was 4 μm, the haze of the film was 20%, and the notched Izod of the injection-molded sample piece was obtained. Impact strength is 3.5kg
f · cm / cm ² .

Comparative Example 7 Using only EVAL (registered trademark) -F101 manufactured by Kuraray,
Notched Iz of a sample piece injection molded as in Example 3.
The od impact strength was 2.1 kgf · cm / cm ² .

Example 6 Instead of 5 g of an ethylene-propylene copolymer having a boronic acid group at the terminal, styrene-isoprene having a boronic acid ethylene glycol ester group in the side chain of Synthesis Example 14 was used instead of 5 g of the ethylene-propylene copolymer having a boronic acid group at the terminal.
A film was obtained in the same manner as in Example 3 except that 5 g of a hydrogenated styrene block copolymer was used. As a result, the average particle size of the block copolymer in the film was 0.4 μm and the haze was 13 μm.
%, And the notched Izod impact strength of the injection-molded sample piece was 23 kgf · cm / cm ² .

COMPARATIVE EXAMPLE 8 A hydrogenated styrene-isoprene-styrene block copolymer (styrene content 35%, MI 2 g /
A film was obtained in the same manner as in Example 3 except that 5 g of 10 minutes and a hydrogenation rate of 95% were used. With Izod impact strength of 4.5 kgf · cm / cm
^{Was 2} .

Example 7 A film was obtained in the same manner as in Example 1 except that 5 g of polystyrene having a boronic acid group at the terminal was used instead of 5 g of polypropylene having a boronic acid group at the terminal. The average dispersed particle size of polystyrene in the film was 0.5 μm, and the haze was 32%.

COMPARATIVE EXAMPLE 9 Except that 5 g of polystyrene having a MI of 2 g / 10 min was used instead of 5 g of polypropylene having a boronic acid group at the end,
When a film was obtained in the same manner as in Example 1, the average polystyrene particle diameter in the film was 5 μm, and the haze was 85 μm.
%Met.

Example 8 A film was produced in the same manner as in Example 1 except that 5 g of polymethyl methacrylate having a boronic acid ethylene glycol ester group at the terminal was used in Synthesis Example 11 instead of 5 g of polypropylene having a boronic acid group at the terminal. As a result, the average dispersed particle size of polymethyl methacrylate in the film was 0.08 μm, and the haze of the film was 8%.

Example 9 A film was prepared in the same manner as in Example 1 except that 5 g of polymethyl methacrylate having a boronic acid ethylene glycol ester group at the terminal was used instead of 5 g of polypropylene having a boronic acid group at the terminal. As a result, the average dispersed particle size of polymethyl methacrylate in the film was 0.1 μm, and the haze of the film was 11%.

Example 10 A film was obtained in the same manner as in Example 1 except that 5 g of polymethyl methacrylate having a borinic acid group at the terminal was used instead of 5 g of polypropylene having a boronic acid group at the terminal. However, the average dispersed particle size of polymethyl methacrylate in the film was 0.1 μm, and the haze of the film was 10%.

Comparative Example 10 A film was obtained in the same manner as in Example 1 except that 5 g of ordinary polymethyl methacrylate having an MI of 0.5 g / 10 min was used instead of 5 g of polypropylene having a boronic acid group at the terminal. The average dispersed particle size of polymethyl methacrylate in the film is 2.5 μm, and the haze of the film is 72 μm.
%Met.

[0086]

[Table 1]

[0087]

[Table 2]

[0088]

[Table 3]

[0089]

[Table 4]

[0090]

[Table 5]

[0091]

[Table 6]

Synthesis Example 3-1 Synthesis of Polypropylene Having a Double Bond at the Terminal A screw diameter of 25 mm provided with a nitrogen inlet tube in the feeder
Polypropylene (MI
0.25 g / 10 min, density 0.90) was supplied, and extruded into pellets under the following conditions. Temperature condition (° C.): C1 / C2 / C3 / C4 / C5 / die = 250/370/370/350/270/210 Discharge rate: 1.45 Kg / h Screw rotation speed: 235 rpm Nitrogen flow rate: 5 L / min The pellets were immersed in hexane for 1 day and dried to obtain a double bond amount of 0.012 meq / g, MI1
2.4 g / 10 min of polypropylene was obtained.

Synthesis Example 3-2 Synthesis of Polypropylene Having Boronate Ethylene Glycol Ester Group In a separable flask equipped with a cooler, stirrer and dropping funnel, 1000 g of polypropylene having a double bond at the end of Synthesis Example 3-1 was prepared. Decalin 200
After degassing by charging 0 g and reducing the pressure at room temperature, the atmosphere was replaced with nitrogen. Trimethyl borate 40
g, 2.9 g of borane-triethylamine complex,
After reacting at 200 ° C. for 4 hours, a distillation apparatus was attached, and 100 ml of methanol was slowly added dropwise. After completion of the dropwise addition of methanol, low boiling impurities such as methanol, trimethyl borate and triethylamine were distilled off by distillation under reduced pressure. Further, 31 g of ethylene glycol was added, and the mixture was stirred for 10 minutes, reprecipitated in acetone, dried and pulverized to obtain a boronic acid ethylene glycol ester group having an amount of 0.1 g.
012 meq / g and MI of 13 g / 10 min were obtained.

Synthesis Example 3-3 Synthesis of ultra low density polyethylene (ULDPE) having a boronic acid ethylene glycol ester group at a terminal: cooler,
In a separable flask with a stirrer and a dropping funnel, an ultra-low-density polyethylene having a double bond at the end (MI 4 g /
10 minutes, density 0.89, double bond amount 0.048 meq /
g) 1000 g and decalin 2500 g were charged, deaerated by reducing the pressure at room temperature, and then replaced with nitrogen. To this were added 78 g of trimethyl borate and 5.8 g of borane-triethylamine complex. After reacting at 200 ° C. for 4 hours, a distillation apparatus was attached, and 100 ml of methanol was further added.
Was slowly added dropwise. After the completion of the dropwise addition of methanol, low-boiling impurities such as methanol and trimethyltriethylamine borate were distilled off under reduced pressure. Further, 31 g of ethylene glycol was added, and the mixture was stirred for 10 minutes, reprecipitated in acetone, dried and pulverized to obtain a boronic acid ethylene glycol ester group amount of 0.27 meq / g, MI3
g / 10 minutes of ultra-low density polyethylene was obtained.

Synthesis Example 3-4 Synthesis of high-density polyethylene having a boronic acid ethylene glycol ester group at a terminal: A high-density polyethylene having a double bond at a terminal in a separable flask equipped with a cooler, a stirrer and a dropping funnel (MI 0.5 g) / 10 min, density 0.957, terminal double bond amount 0.04 meq / g) 80
After 0 g and 2500 g of decalin were charged and degassed by reducing the pressure at room temperature, the atmosphere was replaced with nitrogen. To this, 59 g of trimethyl borate and 4.3 g of a borane-triethylamine complex were added, and after reaction at 200 ° C. for 4 hours, a distillation apparatus was attached, and 100 ml of methanol was slowly added dropwise. After completion of the dropwise addition of methanol, low boiling impurities such as methanol, trimethyl borate and triethylamine were distilled off by distillation under reduced pressure. Further ethylene glycol 31
g, stirred for 10 minutes, reprecipitated in acetone, dried and pulverized to obtain a boronic acid ethylene glycol ester group amount of 0.033 meq / g and an MI of 0.15 g.
A / 10 minute high density polyethylene was obtained.

Example 3-1 A twin-screw extruder having a screw diameter of 25 mmφ was
Synthesis Example 3-3: 20 parts by weight of ultra low density polyethylene having a boronic acid ethylene glycol ester group at the terminal and EVAL L101 manufactured by Kuraray (ethylene content: 27 mol%,
80 parts by weight (EVOH having a saponification degree of 99.7 mol% and an intrinsic viscosity of 1.1 dl / g in water-containing phenol at 30 ° C.) were supplied, and extruded into pellets under the following conditions. Dispersion particle size of ultra low density polyethylene in pellet is 0.1μm
Met. Temperature condition ( ° C. ): C1 / C2 / C3 / C4 / C5 / die = 220/220/220/220/220/220 Discharge rate: 2 kg / h Screw rotation speed: 115 rpm The obtained pellets were tested by injection molding. Make a piece,
The notched Izod impact strength at −40 ° C. of this test piece was 12 kgf · cm / cm ² , and the falling ball impact strength at −40 ° C. was 300 kgf · cm or more.
The falling ball impact strength was measured according to JIS K7211.

Example 3-2 In a twin-screw extruder having a screw diameter of 25 mmφ,
Synthesis Example 3-4 20 parts by weight of high-density polyethylene having a boronic acid ethylene glycol ester group at the terminal and EVAL L101 manufactured by Kuraray (ethylene content 27 mol%, degree of saponification 99.9 mol%, limit in water-containing phenol at 30 ° C.) 80 parts by weight of EVOH having a viscosity of 1.1 dl / g were supplied, and pelletized under the following conditions. The dispersed particle size of the high-density polyethylene in the pellet was 0.2 μm. Temperature condition (° C.): C1 / C2 / C3 / C4 / C5 / die = 240/240/240/240/240/240 Discharge rate: 2 kg / h Screw rotation speed: 115 rpm The obtained pellets were tested by injection molding. Make a piece,
The notched Izod impact strength at −40 ° C. of this test piece was 6.1 kgf · cm / cm ² , and the falling ball impact strength at −40 ° C. was 110 kgf · cm.

Example 3-3 Instead of the ultra-low density polyethylene having a boronic acid ethylene glycol ester group at the terminal, a polypropylene having a boronic acid ethylene glycol ester group at the terminal of Synthesis Example 3-2 was used. The same test as in No. 1 was performed. As a result, the Izod strength was 4.5 kgf · cm / c.
m ² , and the falling ball impact strength was 73 kgf · cm. The dispersed particle size of polypropylene in the pellet is 0.2μ
m.

Comparative Example 3-1 In place of 20 parts by weight of ultra-low-density polyethylene having a boronic acid ethylene glycol ester group at the terminal in Example 3-1 the super-terminal having a double bond used in Synthesis Example 3-3 was used. The same test as in Example 3-1 was performed using low-density polyethylene. As a result, the Izod impact strength was 3.8 kg.
f · cm / cm ² , and the falling ball impact strength is 10 kgf ·
cm. The dispersed particle size of the ultra-low density polyethylene in the pellet was 6 μm.

Comparative Example 3-2 Instead of 20 parts by weight of a high-density polyethylene having a boronic acid ethylene glycol ester group at the terminal in Example 3-2, the high-end polyethylene having a double bond at the terminal used in Synthesis Example 3-4 was used. The same test as in Example 3-2 was performed using the density polyethylene. As a result, the Izod intensity was 3.5 kgf.
Cm / cm ² , and the falling ball impact strength is 5 kgf · cm
/ Cm. The dispersed particle size of the high-density polyethylene in the pellet was 10 μm.

Comparative Example 3-3 Example 3 was repeated, except that the polypropylene having a terminal double bond used in Synthesis Example 3-1 was used instead of the polypropylene having a boronic acid ethylene glycol ester group at the terminal in Example 3-3. The same test as in 3-3 was performed. As a result, the Izod intensity is 2.8 kgf · cm / cm ² ,
The falling ball impact strength was 8 kgf · cm. The dispersed particle size of the polypropylene in the pellet was 5 μm.

Comparative Example 3-4 EVAL L101 manufactured by Kuraray (ethylene content: 27 mol%,
A test piece was prepared by injection molding of EVOH having a saponification degree of 99.7 mol% and an intrinsic viscosity of 1.1 dl / g at 30 ° C. in water-containing phenol, and the notched Izod impact strength of the test piece at −40 ° C. 1.8Kg ・ f ・ cm /
cm ² , and the falling ball impact strength at −40 ° C. is 54 kg.
・ F · cm.

Example 3-4 In a twin-screw extruder having a screw diameter of 25 mmφ,
Synthesis Example 3-3: 10 parts by weight of ultra-low density polyethylene having a boronic acid ethylene glycol ester group at the end, 10 parts by weight of a modified 6-nylon @ poly (caprolactam-laurolactam) copolymer, content of lauriloractam: 35
% By weight, MI (210 ° C., load 2160 g) 8 g / 10
And EVAL L101 made by Kuraray (ethylene content 2
7 mol%, saponification degree 99.7 mol%, EVOH having an intrinsic viscosity of 1.1 dl / g at 30 ° C. in hydrous phenol) 8
0 parts by weight were supplied, and extruded into pellets under the following conditions. Temperature condition (° C.): C1 / C2 / C3 / C4 / C5 / die = 220/220/220/220/220/220 Discharge rate: 2 kg / h Screw rotation speed: 115 rpm The obtained pellet is equipped with a T-die. A 50-μm-thick film was produced using a 20φ extruder. This film piece (5 cm × 1 cm) was subjected to a strain of 5% at 40 ° C.
As a result of immersion in toluene for 30 minutes, no cracks were generated and the stress crack resistance was good.

Example 3-5 A twin-screw segment type extruder having a screw diameter of 25 mmφ was
5 parts by weight of pellets of the blend of Example 3-1; PAX
90 parts by weight of Q450 (high-density polyethylene) manufactured by ON Company and Admer NF450A (adhesive) manufactured by Mitsui Petrochemical
(Maleic anhydride-modified polyethylene) (5 parts by weight) was supplied, and extruded into pellets under the following conditions. Temperature condition (° C.): C1 / C2 / C3 / C4 / C5 / die = 240/240/240/240/240/240 Discharge rate: 2 Kg / h Screw rotation speed: 115 rpm The obtained pellets are thickened by injection molding. A 6.2 mm-thick test piece was prepared and subjected to a notched Izod impact test at −40 ° C .. The Izod impact strength was 14.4 K.
gf · cm / cm ² .

Example 3-6 90 parts by weight of Q450 (high-density polyethylene) manufactured by PAXON, 5 parts by weight of Eval L101 (EVOH) manufactured by Kuraray, and Admer (registered trademark) NF450 manufactured by Mitsui Petrochemical Co., Ltd.
A 5 parts by weight are fed to a 40φ single screw extruder feeder,
Blend pelletization was performed. An extruder I having an inner diameter of 65 mmφ, an extruder II having an inner diameter of 40 mmφ, an extruder III having an inner diameter of 40 mmφ, and an extruder IV having an inner diameter of 40 mmφ are provided.
For I and III, after the molten material branches into two layers,
Resin from the extruder III on the resin layer melt-extruded from IV,
Resin from the extruder II, the type of feedblock type four kinds seven-layer coextrusion apparatus and are sequentially merged resin from the extruder I used, the extruder I Paxon Co. Q450 (high as (P ₁₎ layer resin Density polyethylene), (P
₂ ) 100 parts by weight of the above-mentioned blend pellets as layer resin and 4 parts by weight of high-density polyethylene having a boronic acid ethylene glycol ester group at the end of Synthesis Example 3-4, and (P ₃ ) layer resin in Extruder III as Mitsui Petrochemical Admar (registered trademark) NF450A, Kuraray EVAL L101 is supplied as a (P ₄ ) resin layer to the extruder IV, and co-extrusion is performed at a die temperature of 240 ° C. and a take-up speed of 1 m / min.
_{(P 1) / (P 2} ) / (P 3) / (P 4) / (P 3) /
A laminate of four types and six layers of (P ₁ ) was obtained. The thickness of each layer is 15
0 μm (P ₁ ) / 400 μm (P ₂ ) / 20 μm (P ₃ )
/ 50 μm (P ₄ ) / 20 μm (P ₃ ) / 400 μm (P
₁ ). The film surface of this sheet was good with no wavy pattern and without occurrence of glue.

Comparative Example 3-5 A test similar to that of Example 3-6 was performed without using a high-density polyethylene having a boronic acid ethylene glycol ester group at the terminal in Example 3-6. A wavy pattern was generated, and the film surface was defective.

[0107]

According to the present invention, a resin composition having excellent compatibility and transparency and excellent mechanical properties can be obtained.

[Brief description of the drawings]

FIG. 1 shows a 270 MHz ¹ H-NMR chart of a polypropylene having a terminal boronic acid group obtained in Synthesis Example 2.

FIG. 2 shows 270 MHz ^{1 of} polymethyl methacrylate having a boronic ester group at a terminal obtained in Synthesis Example 11.
1 shows an H-NMR chart.

Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI C08L 101/02 C08L 101/02 (56) References JP-A-4-149236 (JP, A) JP-A-4-21443 (JP, A) JP-A-3-227344 (JP, A) JP-A-2-166146 (JP, A) JP-A-60-238345 (JP, A) JP-A-6-200172 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 23/08 C08L 23/26 C08L 29/04 C08L 47/00 C08L 101/02 C08F 8/42

Claims (7)

(57) [Claims] 1. An ethylene-vinyl alcohol copolymer (A) selected from the group consisting of a boronic acid group, a borinic acid group and a boron-containing group which can be converted to a boronic acid group or a borinic acid group in the presence of water. Ri least a thermoplastic polymer having a single functional group (B) Tona, component and component (a)
Ratio by weight of (B) is 99: 1 to 1: 99 der Ru resin composition. 2. It is selected from the group consisting of an ethylene-vinyl alcohol copolymer (A) and a boronic acid group, a borinic acid group, and a boron-containing group capable of being converted into a boronic acid group or a borinic acid group in the presence of water. Thermoplastic polymer (B) and thermoplastic polymer (C) having at least one functional group
Tona is, ratio by weight of components (A) and component (B) 9
9: 1 to 1:99, and the components (B) and (C)
And weight ratio of component (A) to the total amount of (A):
[(B) + (C) ] is 99: 1 to 1: 99 der Ru resin composition. 3. The component (B) has at least one functional group selected from the group consisting of a boronic acid group, a borinic acid group, and a boron-containing group that can be converted to a boronic acid group or a borinic acid group in the presence of water. 2. A propylene polymer.
Or the resin composition according to 2. 4. The component (B) has at least one functional group selected from the group consisting of a boronic acid group, a borinic acid group, and a boron-containing group that can be converted to a boronic acid group or a borinic acid group in the presence of water. 3. The resin composition according to claim 1, which is an ethylene polymer. 5. Component (B) has at least one functional group selected from the group consisting of a boronic acid group, a borinic acid group, and a boron-containing group that can be converted to a boronic acid group or a borinic acid group in the presence of water. 3. The resin composition according to claim 1, which is a diene polymer. 6. Component (B) is a cyclic ester of a boronic acid group.
Olefin polymer having a functional group consisting of
Item 3. The resin composition according to item 1 or 2. 7. Borane is added to a thermoplastic resin having a double bond.
Reacting the complex with a trialkyl borate
And a boronic acid group, a borinic acid group and the like. And water
That can be converted to a boronic acid or borinic acid group in the presence
At least one functional group selected from the group consisting of contained groups
A method for producing a thermoplastic polymer (B) having the following formula: