JPH06340783A - Resin composition - Google Patents

Abstract

PURPOSE:To provide a resin composition having excellent compatibility, transparency and mechanical properties. CONSTITUTION:The resin composition is composed of (A) an ethylene-vinyl alcohol copolymer and (B) a thermoplastic polymer having at least one functional group selected from among boronic acid group, borinic acid group and a baron-containing group convertible to boronic acid group or borinic acid group in the presence of water. The composition may be incorporated with (C) a thermoplastic polymer in addition to the components A and B.

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 excellent mechanical properties.

[0002]

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

[0003]

[Problems to be Solved by the Invention] However, EVO
Since H and thermoplastic polymers such as polyolefins have a low affinity and poor compatibility, molded products and films made of these blends have a markedly reduced mechanical properties and a greatly reduced transparency. There is a problem. Various methods have been proposed as methods for improving these problems, but none of them are sufficient, and development of new methods is required. Further, a blend of EVOH treated with a boron compound such as boric acid and a blend of a thermoplastic polymer such as polyolefin does not show good compatibility and transparency as will be apparent from Comparative Example 2 described later. Therefore, the object of the present invention is excellent in compatibility and transparency,
Further, it is to provide a resin composition having excellent mechanical properties.

[0004]

[Means for Solving the Problems]
(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 into a boronic acid group or a borinic acid group in the presence of water (B The present invention is achieved by providing a resin composition comprising Further, the above-mentioned object is achieved by providing a resin composition in which the components (A) and (B) are further mixed with a thermoplastic resin (C) other than (A) and (B).

In the present invention, a resin composition having excellent compatibility and good transparency is obtained by blending the components (A) and (B), and further blending the component (C). It is surprising that a melt-kneaded resin composition can be obtained. The cause of this is not clear, but the above-mentioned functional groups of the thermoplastic resin and E
It is presumed that the hydroxyl group of VOH is bonded by the transesterification reaction. In the present invention, the 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. means.

EVOH used in the present invention is ethylene-
It is a saponified vinyl ester copolymer, and the content of ethylene units is not particularly limited, but is selected in the range of 10 to 99 mol%, preferably 15 to 60 mol%, and further 20 to
60 mol% is preferable, and optimally 25-55 mol%. The degree of saponification of the vinyl ester unit of EVOH is selected from the range of 10 to 100 mol%, and is 50 to 1
00 mol% is preferable, 80 to 100 mol% is more preferable, 95 to 100 mol%, and further 99 to 100 mol% is the best. If the saponification degree is too low, the crystallinity may be lowered or the thermal stability during melt molding may be deteriorated. Therefore, the saponification degree is preferably high. Here, vinyl acetate is a typical example of vinyl ester, but other vinyl esters such as vinyl propionate, vinyl pivalate, vinyl valerate, vinyl caprate, and vinyl benzoate are also available. These vinyl esters may be used alone or in combination of two or more. EVOH may be used as a mixture of EVOHs having different ethylene contents, saponification degrees and polymerization degrees. Further, it is important that the EVOH used in the present invention is water-insoluble and thermoplastic.

EVOH may contain other copolymerization components within a range not impairing the object of the present invention. Here, as another component, olefinic monomers such as propylene, 1-butene, isobutene; acrylamide monomers such as acrylamide, N-methylacrylamide, N-ethylacrylamide, N, N-dimethylacrylamide; methacryl 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. , Vinyl ether-based monomers such as dodecyl vinyl ether; allyl alcohol; vinyltrimethoxysilane; N-vinyl-2-pyrrolidone and the like.

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

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 which can be converted into a boronic acid group or a borinic acid group in the presence of water, which is 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, or a boron-containing group that can be converted into a boronic acid group or a borinic acid group in the presence of water is mainly bonded by a boron-carbon bond. It is a thermoplastic polymer bonded to a chain, a side chain or an end. Among these, a thermoplastic polymer having the functional group bonded to a side chain or a terminal is preferable, and a thermoplastic polymer having a terminal bonded to the terminal is most suitable. Here, the term "end" means one end or both ends. Further, the carbon of the boron-carbon bond is derived from the base polymer of the thermoplastic polymer (B) described below or from the boron compound reacted with the base polymer. A preferable example of the boron-carbon bond is a bond between boron and a main chain or an alkylene group at a terminal or side chain.

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

[0011]

[Chemical 1]

Further, the boron-containing group which can be converted into a boronic acid group in the presence of water (hereinafter simply referred to as a boron-containing group) is hydrolyzed in the presence of water and is represented by the above formula (I). If it is a boron-containing group that can be converted to a boronic acid group,
As a typical example, a boronic acid ester group represented by the following general formula (II), a general formula (II
Examples thereof include a boronic acid anhydride group represented by I) and a boronic acid group represented by the following general formula (IV).

[0013]

[Chemical 2]

[0014]

[Chemical 3]

[0015]

[Chemical 4]

[In the formula, X and Y are hydrogen atoms, aliphatic hydrocarbon groups (such as straight-chain or branched alkyl groups having 1 to 20 carbon atoms or alkenyl groups), alicyclic hydrocarbon groups (cyclo Alkyl group, cycloalkenyl group, etc.), aromatic hydrocarbon group (phenyl group, biphenyl group, etc.),
X and Y may be the same group or different. Further, 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 above, and R ¹ , R ² and R 3
³ may be the same group or different. M represents an alkali metal or an alkaline earth metal. Further, the above 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 acid ester group represented by the general formulas (II) to (IV) include a boronic acid dimethyl ester group, a boronic acid diethyl ester group, a boronic acid dipropyl ester group, a boronic acid diisopropyl ester group, and boron. 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 trimethylene glycol ester boronic acid group, neopentyl glycol ester boronic acid group, catechol ester boronic acid group, glycerin ester boronic acid group, trimethylolethane ester boronic acid group; boronic acid anhydride group; boronic acid group And alkaline earth metal bases of boronic acid.

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

[0019]

[Chemical 5]

The boron-containing group which can be converted to a borinic acid group in the presence of water is a boron-containing group which can be converted to a borinic acid group represented by the above formula (V) by being hydrolyzed in the presence of water. Any of them may be used, but as a representative example, 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 general formula (VIII) The borinic acid bases shown may be mentioned.

[0021]

[Chemical 6]

[0022]

[Chemical 7]

[0023]

[Chemical 8]

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

Specific examples of the borinate ester groups represented by the general formulas (V) to (VIII) include X, Z, R ¹ , R ² and R ^3.
Is 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 or a phenyl group. Representative examples thereof include a methylborinic acid group, a methylborinic acid methyl ester group, an ethylborinic acid methyl ester group, a methylborinic acid ethyl ester group, a butylborinic acid methyl ester group, and a 3-methyl-2 butylborinic acid methyl ester group. Among the above functional groups, a boronic acid ester group such as a boronic acid ethylene glycol ester group is particularly preferable from the viewpoint of compatibility with EVOH (A). The boron-containing group which can be converted into a boronic acid group or a borinic acid group in the presence of water is a thermoplastic polymer (B) which is 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
It means a group which can be converted into a boronic acid group or a borinic acid group when hydrolyzed under the condition of 50 ° C.

The content of the functional group is not particularly limited,
0.0001 to 1 meq / g (milliequivalent / g) is preferable, and 0.001 to 0.1 meq / g is particularly preferable.
It is surprising that the compatibility, transparency, etc. of the resin composition are significantly improved by the presence of such a small amount of functional groups.

Typical examples of the base polymer of the thermoplastic polymer (B) include olefin polymers, vinyl polymers and diene polymers which are essentially incompatible with EVOH. Examples of the monomer constituting the olefin polymer, vinyl polymer, and diene polymer include α-olefins such as ethylene, propylene, 1-butene, isobutene, 3-methylpentene, 1-hexene, and 1-octene. Olefinic monomers represented by the group; vinyl ester monomers such as vinyl acetate, vinyl propionate and vinyl pivalate; methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate,
Acrylic ester-based monomers such as octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate; methyl methacrylate, ethyl methacrylate,
Methacrylic acid ester monomers such as butyl methacrylate, octyl methacrylate, dodecyl methacrylate; acrylamide, N-methyl acrylamide, N-
Acrylamide monomers such as ethyl acrylamide and N, N-dimethyl acrylamide; methacrylamide, N
-Methylmethacrylamide, N-ethylmethacrylamide, N, N-dimethylmethacrylamide, and other methacrylamide monomers; vinyl chloride, vinylidene chloride, vinyl fluoride, and other halogenated vinyl monomers; 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. Of these base polymers, especially ethylene-based polymers (ultra low density polyethylene, low density polyethylene,
Medium density polyethylene, high density polyethylene, linear low density polyethylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, ethylene-acrylic acid copolymer metal salt (Na, K, Zn-based ionomer) ), Ethylene-propylene copolymer, etc.}, propylene-based polymer, aromatic vinyl-based polymer (polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-butadiene-acrylonitrile copolymer, styrene- Maleic anhydride copolymer), diene-based polymer {aromatic vinyl-based monomer-diene-based monomer-
Aromatic vinyl-based monomer block copolymer hydrogenated products, polyisoprene, polybutadiene, chloroprene, isoprene-acrylonitrile copolymer (nitrile rubber), isoprene-isobutene copolymer (butyl rubber), etc. are preferred. Can be mentioned.

Suitable melt index (MI) of the thermoplastic polymer (B) used in the present invention (190 ° C., 216
Value measured under 0 g load) 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 the thermoplastic polymer (B) 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 used in the present invention will be described. First production method: An olefin-based polymer having a boronic acid group, a borinic acid group, or a boron-containing group at its terminal is thermally decomposed to introduce a double bond at the terminal, and then a borane complex is added thereto. And a boric acid trialkyl ester.

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

The thermal decomposition is carried out under oxygen-free conditions such as nitrogen atmosphere or vacuum, and the reaction temperature is 300 ° C to 500 ° C.
The temperature and reaction time are 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 the solvent of the olefin polymer having a double bond, the borane complex, the boric acid trialkyl ester, and these three components in a nitrogen atmosphere while stirring. Be done.
As the borane complex, borane-tetrahydrofuran complex, borane-dimethyl sulfide complex, borane-pyridine complex, borane-trimethylamine complex, borane-triethylamine complex and the like are preferable. Among these, borane-triethylamine complex and borane-trimethylamine complex are more preferable. The amount of the borane complex charged is 1/3 equivalent to 10 with respect to the double bond of the olefin polymer.
An equivalent range is preferred. As the boric acid trialkyl ester, boric acid lower alkyl ester such as trimethyl borate, triethyl borate, tripropyl borate, and tributyl borate is preferable. The amount of the trialkyl borate ester charged is preferably in the range of 1 to 100 equivalents with respect to the double bond of the olefin polymer. Although it is not necessary to use a solvent, when it is used, a saturated hydrocarbon solvent such as hexane, heptane, octane, decane, dodecane, cyclohexane, ethylcyclohexane, decalin is preferable.

The reaction for introducing the boronic acid group into the olefin polymer having a double bond is carried out at a reaction temperature of room temperature to 300 ° C.
The reaction is preferably carried out at 100 to 250 ° C. for a reaction time of 1 minute to 10 hours, preferably 5 minutes to 5 hours. The types of boronic acid groups or boron-containing groups can be easily interconverted in 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 the ester group affects the melt index. Generally, the 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.

Second production method of thermoplastic polymer (B); olefin polymer, vinyl polymer having terminal at least one functional group selected from boronic acid group, borinic acid group and boron-containing group, The diene-based polymer radically polymerizes at least one selected from an olefin-based monomer, a vinyl-based monomer, and a diene-based monomer 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 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 borane complex and an olefin in a nitrogen atmosphere, and then adding an alcohol or water. Here, as the thiol having a double bond, 2-propene-1-thiol, 2-methyl-2-propene-1-thiol, 3
-Butene-1-thiol, 4-pentene-1-thiol and the like can be mentioned, among which 2-propene-1-thiol and 2-methyl-2-propen-1-thiol are preferable. As the borane complex, the same ones as described above are used, and among them, the borane-tetrahydrofuran complex is particularly preferable. The addition amount of diborane or borane complex is preferably approximately equivalent to the thiol having a double bond. The reaction conditions are preferably room temperature to 200 ° C. Examples of the solvent include ether solvents such as tetrahydrofuran (THF) and diglyme; saturated hydrocarbon solvents such as hexane, heptane, ethylcyclohexane, decalin and the like. 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 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 the thus obtained thiol having at least one functional group selected from a boronic acid group, a borinic acid group and a boron-containing group, an olefinic monomer, a vinylic monomer, a diene A polymer having the functional group at the terminal is obtained by radically polymerizing at least one selected from the system monomers. As polymerization conditions,
An azo-based or peroxide-based initiator is used, and the polymerization temperature is preferably in the range of room temperature to 150 ° C. The addition amount of the thiol having the functional group is 0.001 per 1 g of the monomer.
The amount of thiol added is preferably about 1 to 1 mmol, and the addition method of thiol is not particularly limited. However, when a monomer such as vinyl acetate or styrene that easily undergoes chain transfer is used, thiol may be fed during polymerization. It is preferable to add a thiol from the beginning when using a substance such as methyl methacrylate that does not easily cause chain transfer.

Third method for producing thermoplastic polymer (B): The thermoplastic resin 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 in the side chain is a boronic acid group or boric 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 above-mentioned olefinic monomer, vinyl monomer and diene monomer are used together. It is obtained by polymerizing. Here, examples of the monomer having at least one functional group selected from a boronic acid group, a borinic acid group, and a boron-containing group include 3-acryloylaminobenzeneboronic acid, 3-methacryloylaminobenzeneboronic acid, and 4-vinyl. Examples thereof include benzeneboronic acid. Further, 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 in the side chain is, for example, acrylic acid, methacrylic acid, itaconic acid, citraconic acid, fumaric acid, and anhydrous. The carboxyl group of a copolymer or graft copolymer of an unsaturated carboxylic acid such as maleic acid and at least one of the above-mentioned olefinic monomer, vinylic monomer and diene monomer is carbodiimide. It can also be obtained by an amide reaction with an amino group-containing boronic acid such as m-aminobenzeneboronic acid with or without a condensing agent such as.

The resin composition of the present invention is the EVOH described above.
(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 mixing ratio of the component (A) and the component (B) is Selected from the range of 99: 1 to 1:99, 9
It is more preferably 5: 5 to 5:99. When imparting heat resistance and mechanical properties to the component (A), (A): (B) is 9
It is preferably 5: 5 to 50:50, and the component (B)
When imparting gas barrier properties and solvent resistance to (A) :( B), it is preferably 5:95 to 50:50. When an olefin polymer, particularly a propylene polymer, is used as the base polymer of the component (B),
As will be apparent from Examples 1 and 2 described later, the hot water resistance is improved, and therefore it is extremely useful as a packaging material for fields requiring hot water resistance, such as retort packaging. Further, as the base polymer of the component (B), an ethylene polymer, a diene polymer {aromatic vinyl monomer (styrene etc.)-Diene monomer (isoprene, butadiene etc.)-Aromatic vinyl monomer When a block copolymer hydrogenated product} is used, as is clear from Examples 3 to 6 described later,
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 component (B), and further a thermoplastic polymer (C) other than component (A) and component (B), especially component (A).
Also included is an embodiment in which a thermoplastic polymer (C) that is essentially incompatible with is blended. In the present invention, even when the thermoplastic polymer (C) which is essentially incompatible with the component (A) is blended, the resin composition having excellent compatibility and transparency is obtained due to the presence of the component (B). This is surprising and this is demonstrated in Example 2 below. In this case, the weight mixing ratio of the components (A), (B) and (C) is
(A): [(B) + (C)] is selected from the range of 99: 1 to 1:99, more preferably 95: 5 to 5:95. When imparting hot water resistance and mechanical properties to the component (A), (A): [(B) + (C)] is 95: 5 to 50: 5.
It is preferably 0, and when imparting gas barrier properties and solvent resistance to the components (B) and (C), (A):
[(B) + (C)] is preferably 5:95 to 50:50. For example, when the base polymer of component (B) and (C) are propylene-based polymers, if the purpose is to improve the gas barrier properties and solvent resistance of the propylene-based polymer, (A): [(B) + (C)] is 5: 95-4
The range of 5:55 is preferable, and for the purpose of imparting hot water resistance to EVOH (A), (A): [(B) + (C)]
Is preferably in the range of 95: 5 to 55:45. The resin (C) used here includes a base polymer of the component (B), particularly a base polymer which is essentially incompatible with EVOH, and one or more of these base polymers may be used. used. 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. As a method of blending these respective components, 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. At that time, blending may be performed by a master batch method. Further, during this blending, other additives such as antioxidants, ultraviolet absorbers, lubricants, plasticizers, antistatic agents, colorants, heat stabilizers {for example, acetic acid, are added as long as 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 (eg Mica, montmalillonite, talc, sericite, glass fiber, bentonite, clay, hydrotalcite, metal oxide, metal hydroxide, metal salt) and the like can be blended.

The resin composition of the present invention can be easily molded by a well-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 product 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, 0.01
It is often in the range of ˜2 μm, preferably 0.01 to 1 μm.

Further, the resin composition of the present invention is a multilayer structure having an EVOH layer and a thermoplastic resin (polyolefin etc.) layer, for example, a multilayer structure comprising an EVOH layer / thermoplastic resin layer, a thermoplastic resin layer / It also includes a mode in which the component (B) used in the present invention is blended with scraps generated when a film, a sheet, a tube, a bottle and the like are manufactured from a multilayer structure composed of an EVOH layer / thermoplastic resin layer. Further, the resin composition of the present invention, other thermoplastic resin,
For example, it is suitable as a multilayer structure including the base polymer of the above-mentioned component (B), and further polyester (polyethylene terephthalate, polybutylene terephthalate, etc.), polyamide, polycarbonate, polyvinyl chloride, polyvinylidene chloride, polyurethane, polyacetal, EVOH, etc. Used. The multilayer structure is molded by a known method such as co-extrusion, co-injection and extrusion coating, and scraps of these molded products can be reused. When the scraps are reused, the resin composition of the present invention can be used. Can be blended in the scrap, or the component (B) used in the present invention can be blended in the scrap. By thermoforming a multi-layer structure, especially a multi-layer sheet or a multi-layer film, it can be made into a container such as a cup, or a desired tube can be formed by blow molding or biaxially stretch blow molding a multi-layer structure, especially a parison. , Can be a bottle.

When a multilayer structure is obtained, 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 adhered. The adhesive resin is not particularly limited as long as it can firmly bond both layers, but an unsaturated carboxylic acid or its anhydride (maleic anhydride, etc.) is used as an olefin polymer or copolymer. Polymer [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.) grafted, hydrogenated styrene-butadiene copolymer acid anhydride (anhydrous Maleic acid, etc.) modified product, acid anhydride modified product of liquid polybutadiene, acid anhydride modified product of ethylene-propylene-diene copolymer and the like, and diene polymer acid anhydride modified product 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 recovery layer / thermoplastic resin layer, thermoplastic resin layer / scrap recovery layer / resin composition Examples include a material layer / scrap recovery layer / thermoplastic resin layer, or a layer in which the above-mentioned adhesive resin layer is interposed between at least one of these layers.

A molded article and a multilayer structure obtained from the above-mentioned resin composition of the present invention are foods required to have gas barrier properties,
It is particularly useful as a packaging material for medicines, medical equipment, clothing and the like. Fuels that require impact resistance (gasoline, etc.)
It is useful as a tube tank or a bottle for agricultural chemicals.

[0046]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In addition, in the following synthesis examples and examples, unless otherwise specified, a ratio means a weight ratio and “%” means “% by weight”. Unless otherwise specified, the melt index (hereinafter abbreviated as MI) is 2160 at a load of 190 ° C.
It is a value measured in g. Also, the intrinsic 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 paraxylene as a solvent. The amount of boronic acid group and its ester group in polypropylene and polyethylene is 270 MHz ¹ H-NMR using a mixed solution of heavy para-xylene: heavy chloroform: ethylene glycol = 8: 2: 0.02 as a solvent.
The amount of boronic acid groups in the resin other than this was determined by deuterated chloroform: ethylene glycol = 10: 0.
Using a mixed solution of 02 as a solvent, 270 MHz ¹
It was quantified by 1 H-NMR. The amount of borinic acid and its ester group was 500 MH using deuterated chloroform as a solvent.
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 end: 200 g of polypropylene {MI (230 ° C., load 2160 g) 0.3 g / 10 minutes} was charged in a separable flask, and the bath temperature was 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 of 80 g / 10 min.

Synthesis Example 2 Synthesis of polypropylene having a boronic acid group at the terminal: 100 g of the polypropylene obtained in Synthesis Example 1 and 200 g of decalin were charged in a separable flask equipped with a condenser and a stirrer, and after nitrogen substitution, 180 C. and nitrogen was introduced into the reactor for 30 minutes. To this was added 5.5 g of trimethyl borate and borane-triethylamine complex 76.
After adding 0 milligram (mg) and performing reaction at 180 degreeC for 4 hours, it cooled to room temperature. The gel polypropylene obtained was washed well with a 1/1 mixture of methanol and acetone, and dried to give a boronic acid group content of 0.025.
A polypropylene (formula (IX) below) having a meq / g and MI of 4 g / 10 min was obtained.

[0049]

[Chemical 9]

270 MHz ¹ H--N 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 produced by reacting the boronic acid in the polymer with ethylene glycol in the solvent.

Synthesis Example 3 Synthesis of ethylene-propylene copolymer having double bond at terminal: propylene content 26% in separable flask,
MI (230 ° C., load 2160 g) 0.7 g / 10 min of ethylene-propylene copolymer 250 g was charged, and after heating at a bath temperature of 280 ° C. under vacuum for 30 minutes, the bath temperature was further set to 32.
By heating to 0 ° C. and heating for 2 hours and 10 minutes, the propylene content is 26%, the amount of double bonds is 0.035 meq /
An ethylene-propylene copolymer having a double bond at the terminal was obtained.

Synthesis Example 4 Synthesis of ethylene-propylene copolymer having a boronic acid group at the end: Synthesis Example 3 in a separable flask equipped with a condenser
30 g of the ethylene-propylene copolymer obtained in 1., borane-pyridine complex 145 mg, tributyl borate 1.1
2 g was charged and nitrogen substitution was carried out. After reacting 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 further purified by repeating this. An ethylene-propylene copolymer having a boronic acid group content of 0.018 meq / g and MI of 1.5 g / 10 min was obtained by vacuum drying at 80 ° C. for 12 hours.

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

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

Synthesis Example 7 Synthesis of 3-mercaptopropylboronic acid ethylene glycol ester: 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. This was charged with 500 ml of THF that had been dried and distilled with benzophenone and metallic sodium, cooled to 0 ° C. in an ice bath, and then stirred while performing boron trifluoride-diethyl ether complex 99.9.
5 g was added dropwise over 30 minutes. 2 hours later at 0 ° C 2
-Propen-1-thiol 45.61 g was added dropwise over 30 minutes. After stirring for 40 minutes, the temperature was raised to 60 ° C. and stirring was further performed for 3 hours. After cooling to 0 ° C., 100 ml of methanol was added dropwise over 40 minutes. 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 distilled under reduced pressure to give 3-mercapto. 4: 1 mixture of boronic acid ethylene glycol ester and 2-mercapto-1-methylethylboronic acid ethylene glycol ester 4
6.7 g were obtained {boiling point 70 ° C. (4 mmHg)}.

Synthesis Example 8 Synthesis of 4- (2-mercaptoethyl) phenylboronic acid ethylene glycol ester: A flask equipped with a dehydration fractionating tube was charged with 2.92 g of 4-vinylphenylboronic acid, 1.38 g of ethylene glycol and 50 ml of benzene. , 80
It heated at 30 degreeC for 30 minutes, and distilled water was removed. To this reaction solution, 3.18 g of thioacetic acid and 47 mg of 2,2′-azobisisobutyronitrile were added, and heated at 75 ° C. for 2 hours.
After distilling off the reaction solvent, the residue was extracted with methylene chloride / sodium hydrogen carbonate aqueous solution, the methylene chloride layer was dried over magnesium sulfate, and then the solvent was distilled off. 5 g of crude 4- (2-acetylthioethyl) phenylboronic acid ethylene glycol ester thus obtained, 20 ml of methanol and 10 ml of triethylamine were placed in a flask, reacted under nitrogen at 65 ° C. for 20 hours, and then distilled under reduced pressure to 4
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 3-mercaptopropyl (3-methyl-2-butyl) borinic acid methyl ester: A flask equipped with a dropping funnel and a stirrer was replaced with nitrogen, and 310 ml of 1N borane THF solution was charged. After cooling to 0 ° C. with an ice bath, 2-methyl-2-butene 21.
74 g was added dropwise over 6 minutes. After 30 minutes 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 stirring was further performed 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 acid ester group at the end: 500 g of styrene in a flask equipped with a stirrer and a reflux condenser and 3-mercaptopropylboronic acid ethylene glycol ester (MPB obtained in Synthesis Example 7).
E) 0.0765 g was charged and deaeration under reduced pressure was performed. 1
After heating to 20 ° C., a styrene solution containing 0.394% MPBE and 0.069% azobiscyclohexanecarbonitrile was first fed at a rate of 7.2 ml and then at a rate of 0.5 ml / min, and after 210 minutes, reaction and feed were performed. Stopped. The polymerization rate at this time was 45%. The polystyrene was purified by reprecipitation with methanol and further dried to give a boronic acid ethylene glycol ester group at the terminal of 0.013 m at MI 2 g / 10 min.
A polystyrene having eq / g was obtained.

Synthesis Example 11 Synthesis of polymethylmethacrylate having a boronic acid ethylene glycol ester group at the terminal: 150 g of methylmethacrylate in a flask equipped with a stirrer and a condenser, and the ethylene glycol 3-mercaptopropylboronic acid obtained in Synthesis Example 7. After degassing by charging 0.876 g of ester and blowing nitrogen, the temperature was raised to 80 ° C. and 0.2 of azobisisobutyronitrile separately prepared.
After the first addition of 1.5 ml of 3% toluene solution, 0.5 ml was added every 30 minutes. After 5 hours, it was cooled and the polymerization was stopped. The polymerization rate at this time was 47%. The obtained polymethylmethacrylate was reprecipitated with methanol and then dried to give a boronic acid ethylene glycol ester group at the terminal at an MI of 0.5 g / 10 min of 0.03 meq /
Polymethyl tacrylate having g (a mixture of the following formula (X) and the following formula (XI) of about 8: 2) was obtained.

[0060]

[Chemical 10]

[0061]

[Chemical 11]

270 MHz ¹ H--N of the obtained polymer
An MR chart is shown, where 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 polymethylmethacrylate having a boronic acid ester group at the terminal: Synthesis Example 8 instead of 3-mercaptopropylboronic acid ethylene glycol 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 of mercaptoethylphenylboronic acid obtained in. As a result, MI 0.5
Polymethylmethacrylate having a boronic acid ethylene glycol ester group of 0.03 meq / g at the end of g / 10 minutes was obtained.

Synthesis Example 13 Synthesis of polymethylmethacrylate having a borinic acid group at the end: 150 g of methylmethacrylate in a flask equipped with a stirrer and a condenser, 3-mercaptopropyl (3-methyl-2-obtained in Synthesis Example 9) (Butyl) borinic acid methyl ester (1.225 g) was charged, and nitrogen was blown thereinto to degas the mixture, and then the temperature was raised to 80 ° C., and a separately prepared 0.23% toluene solution of azobisisobutyronitrile was first prepared. 0.5 ml every 30 minutes after adding 0.5 ml
Was added. After 5 hours, it was cooled and the polymerization was stopped. The polymerization rate at this time was 61%. The obtained polymethylmethacrylate was reprecipitated with methanol and then dried to give a borinic acid group at the end of 0.5 g / 10 min.
Polymethylmethacrylate having 03 meq / g was obtained.

Synthesis Example 14 Synthesis of hydrogenated product of styrene-isoprene-styrene block copolymer having a boronic acid 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 and xylene 100 g were charged in a separable flask, and separately, xylene 20 g, 3-aminophenylboronic acid monohydrate 310 mg, and ethylene glycol 120 mg were prepared by dehydration distillation. A glycol ester / xylene solution was added and heated at 140 ° C. for 3 hours.
After cooling, the precipitate was reprecipitated with methanol containing 0.1% ethylene glycol, purified, and dried to give MI2g / 1.
A hydrogenated styrene-isoprene-styrene block copolymer having 0.028 meq / g of boronic acid ethylene glycol ester group in the side chain at 0 minutes was obtained.

Example 1 Polypropylene 5 having a boronic acid group at the end of Synthesis Example 2
g and Kuraray's EVAL (registered trademark) -F101 (ethylene content 32 mol%, saponification degree 99.5%, EVO having an intrinsic viscosity of 1.1 dl / g at 30 ° C. in water-containing phenol).
Melt kneading was carried out under the following conditions using 45 g of H). Machine used: Plastograph Rotor shape: Roller type Rotational speed: 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 film having a thickness of 100 μm. did. This film was fractured in liquid nitrogen and the fracture surface was 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 diameter of polypropylene was 0.3 μm, and the haze of this press film was 15%. This piece of film is pressed under pressure 110
The film was treated with hot water at ℃ for 30 minutes, but 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 minutes) was used in place of 5 g of a boronic acid group-terminated polypropylene. The unmodified polypropylene has an average dispersed particle size of 5 μm, a film haze of 43%, compatibility,
The transparency was poor. Further, it was partially deformed by the hot water treatment at 110 ° C.

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

Comparative Example 3 Eval (registered trademark) -F101 manufactured by Kuraray Co., Ltd. was used for 220
After hot pressing at 0 ° C., hot water treatment was carried out under the same conditions as in Example 1. As a result, the state was completely denatured and the original shape was not retained.

Example 2 Polypropylene 5 having a boronic acid group at the end of Synthesis Example 2
g, 40 g of unmodified polypropylene (MI1.5 g), Eval (registered trademark) -E105 (ethylene content 44 mol%, saponification degree 99.5%, 3 in hydrous phenol)
Melt kneading was performed under the following conditions using 5 g of an intrinsic viscosity of 0.96 dl / g at 0 ° C. Machine used: Plastograph Rotor shape: Roller type Rotational speed: 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 film having a thickness of 100 μm. did. This film was fractured in liquid nitrogen and the fracture surface was
After extraction with 0 ° C. dimethyl sulfoxide (DMSO), the fracture surface was observed with a scanning electron microscope. As a result, the average dispersed particle diameter of the ethylene-vinyl alcohol copolymer in the film was 0.3 μm, and the haze of this pressed 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 the terminal boronic acid group, and ethylene-vinyl in the film was obtained. The average dispersed particle diameter 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 the ethylene-propylene copolymer having a boronic acid group at the terminal of Synthesis Example 4 was used instead of the polypropylene having a boronic acid group at the terminal. As a result, the average dispersed particle diameter 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 with a small injection molding machine was measured according to the method of JIS K7120, and it was 25 Kgf · cm / cm ² .

Example 4 10 g of an ethylene-propylene copolymer having a boronic acid group at the terminal of Synthesis Example 4 was used in place of the number polypropylene having a boronic acid group at the terminal, and Eval (registered trademark) -F101 manufactured by Kuraray Co., Ltd. (Ethylene content 32 mol%, saponification degree 99.6 mol%, intrinsic viscosity at 30 ° C. in water-containing phenol 1.1 dl / g) In place of 45 g, the same EVAL (registered trademark) 40 g was used. When a film was obtained in the same manner, the average dispersed particle diameter 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 with a small injection molding machine.
When the impact strength was measured according to the method of JIS K7120, it did not break.

Comparative Example 5 Example 4 was repeated except that 10 g of an ethylene-propylene copolymer (propylene content 26%, MI 2 g / 10 minutes) was used instead 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 dispersed particle diameter 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.
It was 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 diameter 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 the 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, and the average dispersed particle size of 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 used. Impact strength is 3.5 kg
It was f · cm / cm ² .

Comparative Example 7 Only Kuraray EVAL (registered trademark) -F101 was used.
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 Styrene-isoprene-having a boronic acid ethylene glycol ester group in the side chain of Synthesis Example 14 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 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
%, And the notched Izod impact strength of the injection-molded sample piece was 23 Kgf · cm / cm ² .

Comparative Example 8 Instead of 5 g of the ethylene-propylene copolymer having a boronic acid group at the terminal, hydrogenated product of 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. As a result, the average particle size of the block copolymer was 5 μm, the haze was 35%, and the notch of the injection-molded sample piece was measured. With Izod impact strength is 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 end of Synthesis Example 10 was used instead of 5 g of polypropylene having a boronic acid group at the end. The average dispersed particle diameter of polystyrene in the film was 0.5 μm, and the haze was 32%.

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

Example 8 A film was prepared in the same manner as in Example 1 except that 5 g of boronic acid group-terminated polypropylene was used instead of 5 g of boronic acid group-terminated polypropylene, and 5 g of polymethylmethacrylate having a boronic acid ethylene glycol ester group was used at the terminal of Synthesis Example 11. As a result, the average dispersed particle diameter of polymethylmethacrylate 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 polypropylene having a boronic acid group at the end was replaced with 5 g of polymethyl methacrylate having a boronic acid ethylene glycol ester group at the end of Synthesis Example 12. As a result, the average dispersed particle diameter of polymethylmethacrylate 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 polymethylmethacrylate having a borinic acid group at the end of Synthesis Example 13 was used instead of 5 g of a polypropylene having a boronic acid group at the end. However, the average dispersed particle diameter of polymethylmethacrylate 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 polymethylmethacrylate 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 diameter of polymethylmethacrylate in the film is 2.5 μm, and the haze of the film is 72.
%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 double bond at the end Screw diameter 25 mm equipped with nitrogen inlet tube in feeder
A polypropylene (MI
0.25 g / 10 minutes, density 0.90) was supplied, and extrusion pelletization was performed 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 Obtained The pellets were dipped in hexane for 1 day and dried to give 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 Boronic Acid Ethylene Glycol Ester Group at the Terminal In a separable flask equipped with a condenser, stirrer and dropping funnel, 1000 g of polypropylene having a double bond at the terminal of Synthesis Example 3-1. Decalin 200
After degassing by charging 0 g and depressurizing at room temperature, nitrogen substitution was performed. Trimethyl borate 40
g, 2.9 g of borane-triethylamine complex are added,
After reacting at 200 ° C. for 4 hours, a distillation tool was attached and 100 ml of methanol was slowly added dropwise. After the addition of methanol was completed, low-boiling-point impurities such as methanol, trimethyl borate, and triethylamine were distilled off by vacuum distillation. Further, 31 g of ethylene glycol was added, and the mixture was stirred for 10 minutes, reprecipitated in acetone, dried and pulverized to give a boronic acid ethylene glycol ester group amount of 0.
A polypropylene of 012 meq / g and MI 13 g / 10 min was obtained.

Synthesis Example 3-3 Synthesis of Ultra Low Density Polyethylene (ULDPE) Having Boronic Acid Ethylene Glycol Ester Group at Terminal: Cooler,
An ultra-low density polyethylene having a double bond at the end of a separable flask equipped with a stirrer and a dropping funnel (MI 4 g /
10 minutes, density 0.89, double bond amount 0.048 meq /
g) 1000 g and decalin 2500 g were charged, and degassing was carried out by reducing the pressure at room temperature, followed by nitrogen substitution. To this, 78 g of trimethyl borate and 5.8 g of borane-triethylamine complex were added, and after reacting at 200 ° C. for 4 hours, a distillation tool was attached, and further 100 ml of methanol was added.
Was slowly added dropwise. After the addition of methanol was completed, low-boiling impurities such as methanol and trimethyltriethylamine borate were distilled off by vacuum distillation. Further, 31 g of ethylene glycol was added, the mixture was stirred for 10 minutes, reprecipitated in acetone, dried and pulverized to give a boronic acid ethylene glycol ester group amount of 0.27 meq / g, MI3.
An ultra low density polyethylene of g / 10 minutes was obtained.

Synthesis Example 3-4 Synthesis of High Density Polyethylene Having Boronic Acid Ethylene Glycol Ester Group at Terminal: In a separable flask equipped with a condenser, stirrer and dropping funnel, high density polyethylene having a double bond at the terminal (MI 0.5 g / 10 minutes, density 0.957, terminal double bond amount 0.04 meq / g) 80
After degassing by charging 0 g and decalin 2500 g and reducing the pressure at room temperature, nitrogen substitution was performed. To this, trimethyl borate (59 g) and borane-triethylamine complex (4.3 g) were added, and after reacting at 200 ° C. for 4 hours, a distillation tool was attached and 100 ml of methanol was slowly added dropwise. After the addition of methanol was completed, low-boiling-point impurities such as methanol, trimethyl borate, and triethylamine were distilled off by vacuum distillation. Further ethylene glycol 31
g, added, stirred for 10 minutes, reprecipitated in acetone, dried and pulverized to give boronic acid ethylene glycol ester group amount 0.033 meq / g, MI 0.15 g
High density polyethylene of / 10 minutes was obtained.

Example 3-1 In a twin-screw type extruder having a screw diameter of 25 mmφ,
20 parts by weight of ultra low density polyethylene having a boronic acid ethylene glycol ester group at the end of Synthesis Example 3-3 and EVAL L101 manufactured by Kuraray (ethylene content 27 mol%,
80 parts by weight of 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. was supplied, and extrusion pelletization was performed 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 = 220/220/220/220/220/220/220 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 of this test piece at −40 ° C. 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 segment type extruder having a screw diameter of 25 mmφ,
20 parts by weight of high-density polyethylene having a boronic acid ethylene glycol ester group at the end of Synthesis Example 3-4 and EVAL L101 manufactured by Kuraray (ethylene content 27 mol%, saponification degree 99.9 mol%, in water-containing phenol at 30 ° C. 80 parts by weight of EVOH having a viscosity of 1.1 dl / g was 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 of this test piece at -40 ° C was 6.1 Kgf · cm / cm ² , and the falling ball impact strength at -40 ° C was 110 Kgf · cm.

Example 3-3 In place of the ultra-low density polyethylene having a boronic acid ethylene glycol ester group at the terminal, polypropylene having a boronic acid ethylene glycol ester group at the terminal in Synthesis Example 3-2 was used, and Example 3-3 was used. The same test as 1 was performed. As a result, Izod intensity was 4.5 Kgf · cm / c
m ² and the falling ball impact strength were 73 Kgf · cm. Dispersion particle size of polypropylene in pellets is 0.2μ
It was 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 at the terminal used in Synthesis Example 3-3. 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 ·
It was 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 high-density polyethylene having a boronic acid ethylene glycol ester group at the terminal in Example 3-2, a high-end 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 density polyethylene. As a result, Izod intensity is 3.5 Kgf
・ Cm / cm ² and falling ball impact strength is 5 kgf ・ cm
Was / cm. The dispersed particle size of the high-density polyethylene in the pellet was 10 μm.

Comparative Example 3-3 Instead of the polypropylene having a boronic acid ethylene glycol ester group at the terminal in Example 3-3, the polypropylene having a double bond at the terminal used in Synthesis Example 3-1 was used. The same test as 3-3 was performed. As a result, the Izod intensity was 2.8 Kgf · cm / cm ² ,
The falling ball impact strength was 8 Kgf · cm. The dispersed particle size of 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 an 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. The Izod impact strength with notch at −40 ° C. of this test piece was 1.8 kg / f / cm /
cm ² , and the falling ball impact degree at -40 ° C is 54 kg.
・ It was f · cm.

Example 3-4 In a twin-screw segment type extruder having a screw diameter of 25 mmφ,
10 parts by weight of ultra-low density polyethylene having a boronic acid ethylene glycol ester group at the end of Synthesis Example 3-3, modified 6-nylon {poly (caprolactam-laurylolactam) copolymer 10 parts by weight, lauriloractam content 35
% By weight, MI (210 ° C., load 2160 g) 8 g / 10
Min} and Kuraray Eval L101 (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 was supplied, and extrusion pelletization was performed 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 pellets obtained were equipped with a T-die. A film having a thickness of 50 μm was manufactured by using a 20φ extruder. With this film piece (5 cm x 1 cm) being subjected to a strain of 5%, 40 ° C
As a result of soaking in toluene for 30 minutes, no crack was generated and the stress crack resistance was good.

Example 3-5 In a twin-screw segment type extruder having a screw diameter of 25 mmφ,
5 parts by weight of pellets of the blend of Example 3-1 PAX
90 parts by weight Q450 (high density polyethylene) manufactured by ON and Admer NF450A (adhesive) manufactured by Mitsui Petrochemical
5 parts by weight of (maleic anhydride-modified polyethylene) was supplied, and extrusion pelletization was performed 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. When a test piece having a size of 6.2 mm was prepared and an Izod impact test with a notch was performed at -40 ° C, the Izod impact strength was 14.4K.
It was 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.
Supply 5 parts by weight of A to a 40φ uniaxial 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.
In I and III, the molten material is branched into two layers, and then the extruder
Resin from extruder III to 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), extruder II (P
₂ ) 100 parts by weight of the above blended pellets as a 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 Mitsui Petrochemical as a (P ₃ ) layer resin for the extruder III. ADMER (registered trademark) NF450A manufactured by Kuraray Eval L101 was supplied as a (P ₄ ) resin layer to the extruder IV, and coextrusion was 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 four-type, six-layer laminate 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 no globbing.

Comparative Example 3-5 The same test as in Example 3-6 was carried out without using the 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 further excellent mechanical properties can be obtained.

[Brief description of drawings]

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

FIG. 2 shows a polymethylmethacrylate having a boronic acid ester group at a terminal obtained in Synthesis Example 11 at 270 MHz ^1.
An H-NMR chart is shown.

Claims (5)

[Claims] 1. An ethylene-vinyl alcohol-based copolymer (A) and a boronic acid group, a borinic acid group, and a boron-containing group which can be converted into a boronic acid group or a borinic acid group in the presence of water. A resin composition comprising a thermoplastic polymer (B) having at least one functional group. 2. An ethylene-vinyl alcohol copolymer (A) and a boronic acid group, a borinic acid group and a boron-containing group which can be 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
A resin composition comprising: 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 boronic acid group or a boron-containing group which can be converted into a boric acid group in the presence of water. A propylene-based 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 boronic acid group or a boron-containing group that can be converted into a boric acid group in the presence of water. The resin composition according to claim 1 or 2, which is an ethylene polymer. 5. 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 boronic acid group or a boron-containing group that can be converted into a boric acid group in the presence of water. The resin composition according to claim 1 or 2, which is a diene polymer.