JP3945140B2 - Process for producing modified ethylene polymer - Google Patents

Description

【００５１】
【表１】

【００５２】
【発明の効果】
本発明によれば、被着材に対する接着力に優れると共に、表面外観にも優れた積層体を得ることができる、不飽和カルボン酸若しくはその無水物変性エチレン系重合体の製造方法を提供することができる。[0001]
  The present invention relates to unsaturated carboxylic acid or anhydride-modified ethylene-based polymerization.the body'sIn more detail, the unsaturated carboxylic acid or its anhydride-modified ethylene-based polymerization can provide a laminate having excellent adhesion to the adherend and excellent surface appearance.the body'sIt relates to a manufacturing method.
[0002]
[Prior art]
Conventionally, olefin polymers such as ethylene polymers and propylene polymers have been used in various packaging by taking advantage of their excellent processability, mechanical properties, water vapor barrier properties, chemical resistance, heat sealing properties, etc.・ Although it is frequently used as a container material, it is inferior in gas barrier properties such as oxygen gas and carbon dioxide gas, content protection such as flavor and fragrance retention properties, etc., and inferior in printability and paintability. There is a drawback.
[0003]
And as a method of improving these defects in the olefin polymer, various resins such as polyester resin, saponified ethylene-vinyl acetate copolymer, polyamide resin, polycarbonate resin, polystyrene resin, aluminum, etc. The form of a laminate with metal foil or the like as an adhering material is adopted. At that time, since the olefin polymer is inferior in adhesion to these adhering materials, the olefin polymer is unsaturated. Modified olefin polymers modified by adding a carboxylic acid or its anhydride are used.
[0004]
As the modified olefin polymer, the olefin polymer is subjected to graft reaction conditions in the presence of a radical generator together with an unsaturated carboxylic acid or an anhydride thereof in a molten state, a solution state, or an aqueous suspension state. Although the modified olefin polymer obtained by any of the methods is known to have a low addition efficiency of the unsaturated carboxylic acid or its anhydride, the addition amount does not increase, while the unsaturated olefin polymer is unsaturated. Although the addition amount can be increased by increasing the amount of carboxylic acid or its anhydride or the amount of radical generator used, the residual amount of unreacted unsaturated carboxylic acid or its anhydride increases, or the olefin polymer. Fish eyes and the like due to gelation of the resin are generated, and unreacted unsaturated olefin polymer is obtained from the resulting modified olefin polymer. A post-treatment method for removing carboxylic acid or its anhydride is also known, but it often involves generation of fish eyes, deterioration of hue, and the like. Therefore, in adhesion force to the adherend and surface appearance, The present condition is that the modified olefin polymer which can satisfy the request | requirement of a market is not obtained.
[0005]
In particular, in the melt kneading method in which the modification can be easily performed by kneading the olefin polymer in a molten state with an extruder or the like without using a solvent or the like, and particularly in the olefin polymer. Thus, the problem is more pronounced in the case of ethylene-based polymers that are cross-linked and have no decrease in molecular weight than propylene-based polymers that are decomposable with respect to radical generators and have a decrease in molecular weight.
[0006]
Further, as a method for producing a modified olefin polymer having excellent adhesion and surface appearance, in the melt kneading method, for example, a molten olefin polymer containing a functional monomer such as maleic anhydride and a radical generator is used. A method of adding an antioxidant to the coalescence (see JP-A-7-216032), a molten olefin polymer containing one of a radically polymerizable monomer such as maleic anhydride and a radical polymerization initiator. (Refer to Japanese Patent Laid-Open No. 7-316239), a method of supplying a solution of an unsaturated carboxylic acid and a radical generator dissolved in a solvent to a molten olefin polymer (Japanese Patent No. 28877747) Etc.) have been proposed, but according to the study by the present inventors, although any improvement is recognized to some extent, Enough to be fully satisfy the determined was found to be not to have obtained improved adhesion and surface appearance.
[0007]
[Problems to be solved by the invention]
  The present invention has been made in view of the above-described prior art. Therefore, the present invention provides an unsaturated carboxylic acid that can provide a laminate having excellent adhesion to an adherend and excellent surface appearance. Or its anhydride-modified ethylene polymerizationthe body'sAn object is to provide a manufacturing method.
[0008]
[Means for Solving the Problems]
  As a result of intensive studies to solve the above-mentioned problems, the present inventors supply unsaturated carboxylic acid or its anhydride in a specific form to a molten ethylene polymer containing a radical generator under a specific state. By finding out that the above object can be achieved, the present invention has been achieved.is there.
[0009]
BookThe present invention is directed to producing a modified ethylene polymer by subjecting an ethylene polymer and an unsaturated carboxylic acid or anhydride thereof to graft reaction conditions in the presence of a radical generator. Using a twin-screw extruder having more than one vent port, supply an unsaturated carboxylic acid or anhydride thereof in a fluid state to an ethylene polymer containing a radical generator having a decomposition rate of 5 to 70%. Then, an unsaturated carboxylic acid or an anhydride thereof is added to the ethylene polymer by melt-kneading at a polymer temperature of 200 to 270 ° C. in the kneading part, and then subjected to a devolatilization treatment from a vent port, A modified ethylene polymer which is melt-extruded by setting the residence time of the polymer in the extruder to 3 times or more of the 99.9% decomposition time of the radical generator at the polymer temperature. Production method, the the gist.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
The modified ethylene polymer of the present invention is obtained by subjecting an ethylene polymer and an unsaturated carboxylic acid or anhydride thereof to graft reaction conditions. Examples of the ethylene polymer include ethylene Homopolymer, ethylene and propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 4,4-dimethyl-1-pentene, 1-hexene, 4-methyl -1-hexene, 1-heptene, 1-octene, 1-decene, 1-octacene and other α-olefins having about 3 to 18 carbon atoms, vinyl acetate, (meth) acrylic acid [where, “(Meth) acryl” means acrylic and methacrylic. , Copolymers with (meth) acrylic acid esters, etc., and specific examples include ethylene homopolymers such as low, medium and high density polyethylene (branched or linear), ethylene- Propylene copolymer, ethylene-1-butene copolymer, ethylene-propylene-1-butene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-1-hexene copolymer, ethylene-1 -Heptene copolymer, ethylene-1-octene copolymer, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid methyl copolymer, ethylene- (meta ) Ethylene resins such as ethyl acrylate copolymer, ethylene- (meth) acrylic acid-methyl (meth) acrylate copolymer, ethylene-propylene copolymer, Len - propylene - non-conjugated diene copolymer, ethylene-1-butene copolymer, ethylene-1-butene - ethylene-based rubber such as non-conjugated diene copolymers. Among them, in the present invention, a resin such as a branched low density ethylene homopolymer or a linear low density ethylene-α-olefin copolymer is preferable.
[0011]
The ethylene polymer preferably has a melt flow rate of 0.01 to 200 g / 10 minutes measured at a temperature of 190 ° C. and a load of 21.18 N in accordance with JIS K7210, preferably 0.1 to 100 g / 10. Minutes are particularly preferred.
[0012]
The ethylene-α-olefin copolymer is, in particular, ethylene and 6 to 12 carbon atoms such as 1-hexene, 4-methyl-1-hexene, 1-heptene, 1-octene and 1-decene. It is composed of α-olefin and has a density of 0.850 to 0.915 g / cm.^ThreeA linear ethylene-α-olefin copolymer having a melt flow rate of 0.01 to 50 g / 10 min under the same conditions as above is preferred.
[0013]
Furthermore, as this linear ethylene-α-olefin copolymer, it is copolymerized in the presence of a metallocene catalyst, rather than being copolymerized in the presence of a conventionally used Ziegler-Natta catalyst or the like. It is preferable that
[0014]
Examples of the ethylene-α-olefin copolymer using a metallocene catalyst include, for example, JP-A Nos. 58-19309, 59-95292, 60-35005, 60-35006, 60-35007, JP-A-60-35008, JP-A-60-35209, JP-A-613030314, JP-A-3-1638308, European Patent Publication No. 420436, US Pat. No. 5,055,438, and International Publication WO91 / 04257. The metallocene catalyst described in the publication No., etc., in particular, the metallocene-alumoxane catalyst is used, or the metallocene compound described in, for example, International Publication WO92 / 01723, etc. reacts with the compound and is stable. For example, gas phase method, slurry method, solution method, high pressure ion Polymerization method such as polymerization method, can preferably be prepared by high pressure ion polymerization method in.
[0015]
Specific examples of the unsaturated carboxylic acid or anhydride thereof include (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and tetrahydrophthalic acid. Unsaturated carboxylic acid or its anhydride is mentioned, Among these, unsaturated dicarboxylic acid or its anhydride, especially maleic acid or its anhydride are preferable.
[0016]
In addition, the graft reaction conditions for the ethylene polymer and the unsaturated carboxylic acid or anhydride thereof are not particularly limited. As will be described later, the radical generator is used in the molten state of the ethylene polymer. It is preferable to perform melt-kneading in the presence of.
[0017]
And the modified ethylene polymer of the present invention has an unsaturated carboxylic acid or anhydride unit addition amount of 0.5 to 2% by weight, the content of unreacted unsaturated carboxylic acid or anhydride thereof is 30 ppm or less, In addition, when the modified ethylene polymer is diluted with the unmodified ethylene polymer so that the addition amount of the unsaturated carboxylic acid or its anhydride unit is 0.25% by weight, the amount of fish eyes is 30 / g. It is essential that:
[0018]
When the addition amount of the unsaturated carboxylic acid or its anhydride unit is less than the above range and the content of the unreacted unsaturated carboxylic acid or its anhydride exceeds the above range, the adhesive strength to the adherend as a modified ethylene polymer If the amount of fish eye exceeds the above range, the adhesion to the adherend as a modified ethylene polymer is inferior, and the surface appearance is poor. In addition, when the addition amount of the unsaturated carboxylic acid or its anhydride exceeds the above range, the content of the unreacted unsaturated carboxylic acid or its anhydride in the above range or / and the amount in the above range of fish eye is achieved. It becomes difficult.
[0019]
The modified ethylene polymer of the present invention can be produced by subjecting the ethylene polymer and the unsaturated carboxylic acid or anhydride thereof to graft reaction conditions in the presence of a radical generator.
[0020]
Here, the amount of the unsaturated carboxylic acid or its anhydride used is preferably 0.5 to 20 parts by weight with respect to 100 parts by weight of the ethylene polymer, and 0.8 to 10 parts by weight. It is particularly preferable to do this. If the amount of unsaturated carboxylic acid or its anhydride used is less than the above range, the amount of addition of unsaturated carboxylic acid or its anhydride in the resulting modified ethylene-based polymer becomes insufficient, and adhesion to the adherend is insufficient. On the other hand, if the amount exceeds the above range, the content of the unreacted unsaturated carboxylic acid or anhydride thereof in the resulting modified ethylene polymer increases, and the adhesion to the adherend also tends to be poor. .
[0021]
In addition, as a radical generator, from the viewpoint of addition reactivity of unsaturated carboxylic acid or its anhydride to an ethylene polymer, the temperature at which the half-life is 1 minute (1 minute half-life temperature) is in the range of 150 to 200 ° C. More specifically, for example, di-t-butyl peroxide (1 minute half-life temperature 193 ° C.), t-butyl cumyl peroxide (178 ° C.), dicumyl peroxide ( 171 ° C.), 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (179 ° C.), 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3 (193 ° C.), dialkyl peroxides, t-butyl peroxyacetate (159 ° C.), t-butyl peroxylaurate (165 ° C.), t-butyl peroxybenzo (166 ° C), di-t-butyldiperoxyphthalate (159 ° C), t-butylperoxyisopropyl carbonate (158 ° C), 2,5-dimethyl-2,5-di (benzoylper) Peroxyesters such as oxy) hexane (162 ° C.), 2,5-dimethyl-2,5-di (benzoylperoxy) hexyne-3 (162 ° C.), methyl ethyl ketone peroxide (171 ° C.), cyclohexanone Examples thereof include ketone peroxides such as peroxide (at 174 ° C.), and two or more of these may be used in combination.
[0022]
Among them, an organic solvent having a half-life of 0.1 to 10 times the residence time of the ethylene polymer at the kneading temperature (polymer temperature in the kneading section described later) used in the modification described later. An oxide is preferable, and specifically, for example, di-t-butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl. Particularly preferred are dialkyl peroxides such as -2,5-di (t-butylperoxy) hexyne-3.
[0023]
Here, the amount of the radical generator used is preferably 0.01 to 20 parts by weight, more preferably 0.05 to 10 parts by weight with respect to 100 parts by weight of the ethylene polymer. Particularly preferred. If the amount of the radical generator used is less than the above range, the amount of the unsaturated carboxylic acid or its anhydride added in the resulting modified ethylene polymer becomes insufficient, and the adhesive force to the adherend tends to be inferior, When the range is exceeded, the resulting modified ethylene polymer tends to have poor surface appearance due to an increase in fish eyes and the like due to gelation and the like.
[0024]
The method for producing a modified ethylene polymer of the present invention uses a twin screw extruder having two or more raw material supply ports and one or more vent ports, and the decomposition rate of the unsaturated carboxylic acid or its anhydride is reduced. The unsaturated carboxylic acid or its anhydride is added to the ethylene polymer by supplying it in a fluid state to the ethylene polymer containing the radical generator of 5 to 70%, and melt-kneading the mixture. .
[0025]
The twin-screw extruder is usually a barrel provided with a raw material supply port, a vent port, and a jacket, and a plurality of grooves are engraved on the surface and rotated in the same direction or in different directions. It is composed of a screw and a die attached to the tip of the extruder, and a kneading section composed of a plurality of kneading disks is provided in the middle of the screw in a form that meshes with each other or a form that does not mesh with each other. As an extruder having a high kneading function, for example, “TEXα” series is commercially available from Nippon Steel Works, and “TEM-SS” series is available from Toshiba Machine Co., Ltd.
[0026]
The twin screw extruder in the present invention has 2 to 3 raw material supply ports and 2 to 3 vent ports, and the ratio (L / D) of the screw length (L) to the screw diameter (D). 10 to 50, the rotational direction is the same direction, and the meshing form is partial or complete meshing type is preferable.
[0027]
And in this invention, supply of the unsaturated carboxylic acid or its anhydride to the twin-screw extruder is with respect to the ethylene polymer containing the radical generator whose decomposition rate is 5-70%. And it is essential to make it fluid. Further, the temperature of the ethylene polymer at that time is preferably in the range of 100 to 250 ° C.
[0028]
In addition, in order to supply unsaturated carboxylic acid or its anhydride with respect to the ethylene polymer containing the radical generator whose decomposition rate is 5-70% here, specifically, for example, , A method of supplying an ethylene polymer and a radical generator from a first raw material supply port of a twin-screw extruder, and an unsaturated carboxylic acid or anhydride thereof from a second raw material supply port, or a first raw material supply A preferable method includes a method in which an ethylene polymer is supplied from the mouth and a radical generator is supplied from the second raw material supply port, and an unsaturated carboxylic acid or an anhydride thereof is supplied from the third raw material supply port. At that time, the unsaturated carboxylic acid or its anhydride or radical generator is supplied to the raw material supply port after the second raw material supply port by press-fitting with a plunger pump or the like.
[0029]
In addition, as the fluid form of the unsaturated carboxylic acid or its anhydride, specifically, for example, the unsaturated carboxylic acid or its anhydride is dissolved in a molten state or a solvent heated to a melting point or higher. Examples include a solution form.
[0030]
Furthermore, in the method for producing the modified ethylene polymer of the present invention, after supplying the unsaturated carboxylic acid or its anhydride, the polymer temperature in the kneading part is melt-kneaded at 200 to 270 ° C., and then from the vent port. After performing the devolatilization treatment, melt-extruding the residence time in the twin-screw extruder of the ethylene polymer as 3 times or more of the 99.9% decomposition time of the radical generator at the polymer temperature in the kneading part. Is required.
[0031]
Here, the devolatilization treatment from the vent port is preferably performed by gradually increasing the degree of vacuum in a reduced pressure range of 0.1 to 85 kPa from the vent ports provided at a plurality of locations. The residence time is set in the range of 0.1 to 10 minutes.
[0032]
As described above, the decomposition rate of the radical generator when the unsaturated carboxylic acid or its anhydride is supplied, the form when the unsaturated carboxylic acid or its anhydride is supplied, the temperature of the polymer in the kneading part (kneading temperature), the kneaded product If any of the devolatilization treatment and the residence time of the ethylene polymer does not satisfy the above requirements, the resulting modified ethylene polymer will have poor adhesion to the adherend, or / And the surface appearance is inferior.
[0033]
The modified ethylene polymer produced by the production method of the present invention has a ratio of the melt flow rate of the modified ethylene polymer to the melt flow rate of the ethylene polymer before modification in the above-described conditions of 0.05 to A range of 1.0 is preferred.
[0034]
Further, in the modified ethylene polymer of the present invention and the production method thereof, in addition to the ethylene polymer, the radical generator, and the unsaturated carboxylic acid or anhydride thereof, a range that does not impair the effects of the present invention. In other thermoplastic resins and rubbers, antioxidants, light stabilizers, ultraviolet absorbers, nucleating agents, neutralizing agents, antistatic agents, lubricants, antiblocking agents, fluidity improvers, plasticizers, Release agents, flame retardants, colorants, dispersants, fillers, and the like may be used.
[0035]
In addition, the ethylene polymer, or further the radical generator, or other resin or rubber used as necessary, additives, etc., are usually tumbler blender, ribbon blender, before supply to the twin screw extruder, Mix evenly with a V-type blender or Henschel mixer.
[0036]
The modified ethylene polymer obtained by the production method of the present invention is usually subjected to sequential extrusion laminating, sandwich extrusion laminating, coextrusion on an adherend with or without an anchor coating agent by a conventionally known method. A laminated body is formed by a method of laminating, a method of co-extrusion together with an adherent resin, a method of preliminarily forming a film and thermally fusing the adherend resin.
[0037]
Examples of the adherend include various thermoplastic resins such as polyamide resin, polyester resin, saponified ethylene-vinyl acetate copolymer, polyolefin resin, polycarbonate resin, polystyrene resin, and acrylic resin. And metal foils and plates such as aluminum, copper, lead, and stainless steel, and paper.
[0038]
【Example】
EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist.
[0039]
Example 1
A twin screw extruder (spindle diameter: 32 mm, L / D 42.5, manufactured by Nippon Steel Works) "TEX30"), a linear low density ethylene-α-olefin copolymer resin (density 0.898 g / cm^Three, 100 parts by weight of melt flow rate 15 g / 10 min) and 0.065 parts by weight of 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (“Perhexa 25B” manufactured by NOF Corporation) , Mixed with a Henschel mixer, supplied to the twin-screw extruder from the first raw material supply port, and subsequently melted to about 70 ° C. from the second raw material supply port set at 185 ° C. as the resin temperature immediately below The maleic anhydride is added to the ethylene-α-olefin copolymer resin by adding 1.3 parts by weight of maleic anhydride and melt-kneading in a kneading part set at 245 ° C. as the resin temperature, , After devolatilization from the first vent port having a reduced pressure of 1.3 kPa and the second vent port having a reduced pressure of 1.3 kPa, the residence time in the extruder of the ethylene-α-olefin copolymer resin Was melt-extruded into a strand shape so as to be 15 seconds, cooled, solidified, and cut to prepare a pellet-like maleic anhydride-modified ethylene-α-olefin copolymer resin.
[0040]
Here, the residence time of the resin to the second raw material supply port supplied with maleic anhydride is 5 seconds, and the decomposition rate of the radical generator at the maleic anhydride supply position calculated by the following method is 10%. Met. Also, the 99.9% decomposition time of the radical generator at the resin temperature of 245 ° C. in the kneading part, calculated by the following method, was 3 seconds, and therefore the resin residence time of 15 seconds was 5 times that. .
[0041]
Decomposition rate of radical generator
1 minute half-life temperature T of radical generator_1/2From A.C. (179.degree. C.) according to the following equation (1): Arrhenius equation [k = Aexp (-E / RT), where k is the rate constant, A is the frequency factor, E is the activation energy, and R is the gas constant. , T is the absolute temperature. ], The temperature T of the resin when maleic anhydride is supplied (185 ° C.), and the resin residence time t until maleic anhydride is supplied₁From the second (5 seconds), the decomposition rate (%) of the radical generator at the maleic anhydride supply position was calculated by the following formula (2) and the following formula (3).
A = {(ln2) / 60} / exp {-E / R (T_1/2+273)} (1)
B = exp [t₁Aexp {−E / R (T + 273)}] (2)
Decomposition rate of radical generator (%) = 1- (1 / B) (3)
[0042]
99.9% decomposition time of radical generator
From the temperature T ° C. (245 ° C.) of the resin in the kneading part, the following formula (4): [In the formula (4), C and D are constants specific to the radical generator. According to the catalog of the company, C = −0.076 and D = 17.44. ], The half-life t of the radical generator at the temperature_1/2Find the second and its half-life t_1/2From the second, the 99.9% decomposition time (second) of the radical generator was calculated by the following formula (5).
lnt_1/2= CT + D (4)
99.9% decomposition time (seconds) = 3t_1/2/ Log2 (5)
[0043]
About the obtained maleic anhydride-modified ethylene-α-olefin copolymer resin, melt flow rate, addition amount and addition rate of maleic anhydride units, content of unreacted maleic anhydride, and the method shown below, and The amount of fish eye was measured and the results are shown in Table 1.
Melt flow rate
Measurement was performed at a temperature of 190 ° C. and a load of 21.18 N in accordance with JIS K7210.
[0044]
Amount and rate of addition of maleic anhydride units
A film having a thickness of 100 μm was prepared from the modified resin pellets by hot pressing, the carbonyl group absorption was measured by an infrared absorption spectrum, and the total amount of maleic anhydride in the modified resin was determined from a separately prepared calibration curve. On the other hand, after the modified resin pellet was dissolved in boiling xylene, it was reprecipitated in acetone, and the precipitate was filtered and vacuum-dried at 80 ° C. for 6 hours. The addition amount of maleic anhydride units was determined, and the addition rate relative to the total maleic anhydride amount was calculated.
[0045]
Unreacted maleic anhydride content
About 20 g of the modified resin pellet is precisely weighed, and reflux extraction is performed for 8 hours using 100 ml of acetone as an extraction solvent. The extract is air-dried and then dissolved in 5 ml of 0.1 M sodium dihydrogen phosphate (pH 2). For the filtrate filtered through a 45 μm filter, high performance liquid chromatography (“HPLC 8020 series” manufactured by Tosoh Corporation, column uses “TSK-Gel ODS-120T” manufactured by Tosoh Corporation, 150 mm × 4.6 mm, particle size 5 μm) Was quantified.
[0046]
Fisheye amount
Using an unmodified linear low density ethylene-α-olefin copolymer resin (melt flow rate 2 g / 10 min), the addition amount of maleic anhydride units in the diluted resin is 0.25% by weight. The modified resin was diluted so that a film having a thickness of 30 μm was blown from the diluted resin at a molding temperature of 170 ° C., and then 100 cm from the film.²Were cut out, the number of fish eyes having a size of 0.2 to 0.5 mm was counted, and the number was converted to the number per unit weight g.
[0047]
Further, with respect to the obtained maleic anhydride-modified ethylene-α-olefin copolymer resin, the adhesion strength to the adherend was measured by the method shown below, and the results are shown in Table 1.
[0048]
Adhesive strength to adherend
25% by weight modified resin, high density ethylene homopolymer resin (density 0.950 g / cm^Three, Melt flow rate 4 g / 10 min) 25% by weight, linear low density ethylene-α-olefin copolymer resin (density 0.920 g / cm^Three, 25% by weight, melt flow rate 2 g / 10 min), linear low density ethylene-α-olefin copolymer resin (density 0.898 g / cm^Three, Melt flow rate 15 g / 10 min) 25% by weight of resin composition and saponified ethylene-vinyl acetate copolymer, molding temperature 190 ° C., molding speed 30 m / min, 50 m / min, or 70 m / min A two-layer laminated film of a modified resin-containing resin composition layer of 35 μm and an ethylene-vinyl acetate copolymer saponified product layer of 35 μm was subjected to inflation molding under the condition of an air gap of 250 mm. From this, a test piece having a width of 10 mm and a length of 120 mm was cut out, and a T-type peel test was performed with a shopper type tensile tester in accordance with JIS K6854 at a peel rate of 500 mm / min to measure peel strength.
[0049]
  Examples 2 to 4, Comparative Examples 1 to6
  Use amount of radical generator, use amount and supply position of maleic anhydride, residence time of resin to raw material supply port supplying maleic anhydride, resin temperature at the raw material supply port, supply form of maleic anhydride, kneading part In the same manner as in Example 1, except that the resin temperature, the presence or absence of devolatilization treatment from the vent port, and the residence time of the resin in the extruder were changed as shown in Table 1, maleic anhydride-modified ethylene- An α-olefin copolymer resin is produced, and the melt flow rate, the addition amount and addition rate of maleic anhydride units, the content of unreacted maleic anhydride, and the amount of fish eye are measured. The adhesive strength was measured and the results are shown in Table 1.
[0050]
[Table 1]

[0051]
[Table 1]

[0052]
【The invention's effect】
  According to the present invention, an unsaturated carboxylic acid or its anhydride-modified ethylene-based polymerization can be obtained, which can provide a laminate having excellent adhesion to an adherend and excellent surface appearance.the body'sA manufacturing method can be provided.

Claims (5)

  In producing a modified ethylene polymer by subjecting an ethylene polymer and an unsaturated carboxylic acid or anhydride thereof to graft reaction conditions in the presence of a radical generator, two or more raw material supply ports and one or more raw materials are supplied. Using a twin-screw extruder having a vent port, an unsaturated carboxylic acid or anhydride thereof is supplied in a fluid state to an ethylene polymer containing a radical generator having a decomposition rate of 5 to 70%, and kneaded. The polymer temperature at 200 parts is melt-kneaded at 200 to 270 ° C. to add the unsaturated carboxylic acid or its anhydride to the ethylene polymer, and then subjected to devolatilization from the vent port. A modified ethylene system characterized by being melt-extruded with a residence time in the extruder of 3 times or more of the 99.9% decomposition time of the radical generator at the polymer temperature Manufacturing method of the united. The ethylene polymer and radical generator are supplied from the first raw material supply port of the twin-screw extruder, or the ethylene polymer is supplied from the first raw material supply port and the radical generator is supplied from the second raw material supply port. In addition, the method for producing a modified ethylene polymer according to claim 1 , wherein the unsaturated carboxylic acid or an anhydride thereof is supplied from a raw material supply port after the second raw material supply port. The method for producing a modified ethylene polymer according to claim 1 or 2 , wherein the unsaturated carboxylic acid or its anhydride is supplied to an ethylene polymer having a temperature of 100 to 250 ° C. The method for producing a modified ethylene polymer according to any one of claims 1 to 3 , wherein the fluid unsaturated carboxylic acid or anhydride thereof is in a molten state in which the unsaturated carboxylic acid or anhydride is heated to a melting point or higher. . The method for producing a modified ethylene polymer according to any one of claims 1 to 4 , wherein the ethylene polymer is an ethylene homopolymer or an ethylene-α-olefin copolymer.