KR101199282B1 - Resin composition, foamed article and laminated article - Google Patents

Abstract

Resin composition whose content of following component (i) is 99-30 weight%, and content of following component (ii) is 1-70 weight%, the layer which consists of materials different from the pressurized foam molded object of this resin composition, and this pressurized foam molded object layer. Laminate obtained by laminating:

(Iii) an ethylene-α-olefin-based copolymer having an ethylene monomer unit and an α-olefin monomer unit having 3 to 20 carbon atoms, a melt flow rate of 0.01 to 5 g / 10 minutes, and an activation energy of a flow of 30 kJ / mol or more. ,

(Ii) An ethylene-unsaturated ester copolymer having an unsaturated ester monomer unit and an ethylene monomer unit.

Description

RESIN COMPOSITION, FOAMED ARTICLE AND LAMINATED ARTICLE}

Patent Document 1: Japanese Patent Application Laid-Open No. 11-151101

This invention relates to the laminated body which has a resin composition, its pressurized foam molded object, and the layer of this foam.

The laminated body which laminated | stacked the foamed molded object which consists of polyethylene-type resin, and this and the molded object which consists of non-polyethylene-type resin is used widely as daily miscellaneous goods, a flooring material, a sound insulation material, and a heat insulating material, For example, pressurizing an ethylene-vinyl acetate copolymer Soles and the like formed by laminating an upper window obtained by pressurizing and foaming a member obtained by cutting a molded article formed by foam molding into a desired shape and a lower window made of styrene-butadiene rubber or the like are known (for example, Patent Document 1). Reference).

However, the above-mentioned foamed molded article is not sufficiently satisfactory in the balance between light weight and rigidity, and it is not necessarily satisfactory even in a laminate in which a molded article made of this and a non-polyethylene resin is laminated.

Under these circumstances, an object of the present invention is to laminate a resin composition which provides a pressure-foamed molded article having excellent balance between light weight and rigidity, a pressure-foamed molded article thereof, and a layer made of a material different from the layer of the pressure-foamed molded article and the foamed layer. It is to provide one laminated body.

In addition, another object of the present invention is to provide a laminate excellent in interlayer adhesion including a resin composition for providing a high-pressure foamed molded article having high strength, the foamed molded article and the layers of the pressurized foamed molded article.

That is, this invention contains following component (i) and (ii), makes the total amount of component (i) and (ii) 100 weight%, content of component (i) is 99-30 weight%, and The content of (ii) relates to a resin composition having 1 to 70% by weight:

(Iii) a monomer unit based on ethylene and a monomer unit based on an α-olefin having 3 to 20 carbon atoms, a melt flow rate of 0.01 to 5 g / 10 minutes, and an activation energy of the flow of 30 kJ; Ethylene-α-olefin-based copolymer that is / mol or more,

(Ii) An ethylene-unsaturated ester copolymer having monomer units based on at least one unsaturated ester selected from carboxylic acid vinyl esters and unsaturated carboxylic acid alkyl esters and monomer units based on ethylene.

Moreover, this invention relates to the pressure-foaming molded object formed by pressure-foaming the said resin composition.

And this invention relates to the laminated body formed by laminating | stacking the layer which consists of said pressurized foam molded object, and the layer which consists of a non-ethylene-type resin material.

According to this invention, the laminated body containing the resin composition which provides the pressurized foamed molded object excellent in the balance of light weight and rigidity, its pressurized foamed molded object, and the foamed layer of this pressurized foamed molded object can be provided. Moreover, according to this invention, the resin composition which provides the pressurized foamed molded object which is further excellent in intensity | strength, the pressurized foamed molded object, and the laminated body containing the same can also be provided.

Carrying out the invention  Best form for

The ethylene-α-olefin-based copolymer of component (iii) is an ethylene having a monomer unit based on ethylene and a monomer unit based on an α-olefin having 3 to 20 carbon atoms (hereinafter simply referred to as an α-olefin). System copolymer. Examples of the α-olefin include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, and the like, and preferably 1-butene and 1-hexene.

Examples of the ethylene-α-olefin copolymer of component (i) include ethylene-1-butene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-1-hexene copolymer and ethylene-1-octene copolymer , Ethylene-1-decene copolymer, ethylene-1-butene-4-methyl-1-pentene copolymer, ethylene-1-butene-1-hexene copolymer, ethylene-1-butene-1-octene copolymer and the like These are ethylene-1-butene copolymer, ethylene-1-hexene copolymer, and ethylene-1-butene-1-hexene copolymer from a viewpoint of strength, More preferably, ethylene-1- Butene-1-hexene copolymer and ethylene-1-hexene copolymer.

It is preferable that the ethylene-alpha-olefin type copolymer of component (i) makes content of all the monomeric units in the copolymer 100, and contains 50 weight% or more of monomeric units based on ethylene. In addition, since the density of a copolymer increases when content of ethylene increases, it is preferable to make it into 930 kg / m <3> or less as mentioned later.

Melt flow rate (MFR) of the ethylene-alpha-olefin type copolymer of component (i) is 0.01-5 g / 10min. If the MFR is less than 0.01 g / 10 minutes, the foaming ratio may decrease, preferably 0.05 g / 10 minutes or more, and more preferably 0.1 g / 10 minutes or more. In addition, when the MFR exceeds 5 g / 10 minutes, the interlayer adhesion of the multilayer molded body may be lowered, preferably 2 g / 10 minutes or less, more preferably 0.8 g / 10 minutes or less, and even more preferably. Is 0.6 g / 10 min or less. The MFR is measured by the A method under the conditions of a temperature of 190 ° C. and a load of 21.18 N in accordance with JIS K7210-1995.

The ethylene-α-olefin type copolymer of component (i) is a copolymer whose activation energy (Ea) of a flow is 30 kJ / mol or more. If the Ea is too low, the bubble properties may be nonuniform and the appearance may deteriorate. As Ea from a viewpoint of raising a bubble property, Preferably it is 40 kJ / mol or more, More preferably, it is 50 kJ / mol or more, More preferably, it is 55 kJ / mol or more. In addition, the Ea is preferably 100 kJ / mol or less, and more preferably 90 kJ / mol or less from the viewpoint of smoothing the surface of the pressure-foamed molded body.

Activation energy (Ea) of the flow is a dependency indicating the angular frequency (unit: rad / sec) dependence of the melt complex viscosity (unit: Pa · sec) at 190 ° C. based on the principle of temperature-time superposition. It is a numerical value calculated by the Arrhenius equation from the shift factor (a _T ) at the time of creating the master curve which shows the following, It is the value calculated | required by the method shown below. That is, the melt complex viscosity-angular frequency curve of the ethylene-α-olefin copolymer at 130 ° C, 150 ° C, 170 ° C, and 190 ° C, respectively (T, unit: ° C) (the unit of the melt complex viscosity is Pa. sec, the unit of angular frequency is rad / sec), based on the principle of temperature-time superposition, the melt complex viscosity of the ethylene copolymer at 190 ° C. for each viscosity-angular frequency curve at each temperature (T) viscosity - obtaining the shift factor (a _T) at each temperature (T) is obtained when sikyeoteul superposed on each of the frequency curve, and the respective temperature (T), the least square from the shift factor (a _T) at each temperature (T) The first approximation equation (following formula (I)) of [ln (a _T )] and [l / (T + 273.16)] is calculated by the method. Next, Ea is calculated | required from the slope (m) of the linear formula and following formula (II).

ln (a _T ) = m (l / (T + 273.16)) + n (I)

Ea = | 0.008314 × m | (II)

a _T : shift factor

Ea: activation energy of the flow (unit: kJ / mol)

T: Temperature (unit: ℃)

The calculation may use commercially available calculation software, and Rhios V.4.4.4 by Rheometrics, etc. is mentioned as this calculation software. In addition, the shift factor (a _T ) moves both logarithmic curves of the melt complex viscosity-angular frequency at each temperature (T) in the log (Y) =-log (X) axis direction (but melts the Y axis). Complex viscosity, the X-axis is the angular frequency), and the amount of shift when superimposed on the melt complex viscosity-angular frequency curve at 190 ° C., at which the melt complex viscosity-angular frequency at each temperature T is superimposed. Both algebraic curves shift the angular frequency by a _T times and the melt complex viscosity by 1 / a _T times for each curve. In addition, the correlation coefficient when (I) Formula is calculated | required by the least squares method from the value of four points of 130 degreeC, 150 degreeC, 170 degreeC, and 190 degreeC is 0.99 or more normally.

The measurement of the melt complex viscosity-angular frequency curve is performed using a viscoelasticity measuring device (for example, Rheometrics Mechanical Spectrometer RMS-800 manufactured by Rheometrics, etc.), and usually geometry: parallel plate, plate diameter: 25 mm, plate spacing: 1.5 It measured on the conditions of -2 mm, a strain: 5%, and an angular frequency: 0.1-100 rad / sec. In addition, the measurement is performed under nitrogen atmosphere, and it is preferable to mix | blend an appropriate amount (for example, 1000 wt-ppm) antioxidant with the measurement sample previously.

The density of the ethylene-α-olefin-based copolymer of component (i) is preferably 890 kg / m 3 or more, from the viewpoint of increasing the secondary workability such as the rigidity of the pressure-foaming molded product, the cutting of the pressure-foamed molded product, and more preferably. Is 900 kg / m 3 or more, and more preferably 905 kg / m 3 or more. In addition, the density is preferably 930 kg / m 3 or less, and more preferably 925 kg / m 3 or less from the viewpoint of increasing the lightness of the pressurized foamed molded article. In addition, the density is measured by the underwater substitution method of JISK7112-1980 after performing annealing of JISK6760-1995.

As a manufacturing method of the ethylene-alpha-olefin type copolymer of component (i), the following crude catalyst carrier (A), a crosslinking bisindenyl zirconium complex (B), and an organoaluminum compound (C) are made to contact The method of copolymerizing ethylene and the C3-C20 alpha olefin in presence of the catalyst obtained is mentioned.

The cocatalyst carrier (A) is (a) diethylzinc, (b) fluorinated phenol, (C) water, (d) silica and (e) trimethyldisilazane {((CH ₃ ) ₃ Si) ₂ NH } Is a carrier obtained by contacting.

Although the usage-amount of each component of said (a), (b), (c) is not restrict | limited, Component ratio (a): component (b): component (c) = 1: y: z It is preferable that y and z satisfy the following formula.

2-y-2z≤1

As y in the said formula, Preferably it is the number of 0.01-1.99, More preferably, it is the number of 0.10-1.80, More preferably, it is the number of 0.20-1.50, Most preferably, it is the number of 0.30-1.00.

In addition, as the quantity of the component (d) used with respect to the component (a), the number of moles of zinc atoms contained in the particles obtained by the contact of the component (a) and the component (d) is 0.1 mmol per 1 g of the particles. It is preferable that it is the quantity used above, and it is more preferable that it is quantity which becomes 0.5-20 mmol. As the quantity of the component (e) used with respect to a component (d), it is preferable that it is an amount used as component (e) 0.1 mmol or more per 1 g of component (d), and it is more preferable that it is an amount used as 0.5-20 mmol.

As the crosslinked bisindenyl zirconium complex (B), racemic-ethylenebis (1-indenyl) zirconium dichloride and racemic-ethylenebis (1-indenyl) zirconium diphenoxide are preferable.

Moreover, as an organoaluminum compound (C), Preferably they are triisobutyl aluminum and tri n-octyl aluminum.

The usage-amount of a crosslinking bisindenyl zirconium complex (B) is per 5 g of cocatalyst carriers (A), Preferably it is 5 * 10 <^-6> -5 * 10 <^-4> mol. Moreover, as an usage-amount of an organoaluminum compound (C), Preferably, it is the quantity which becomes 1-2000 mol of aluminum atoms of an organoaluminum compound (C) per 1 mol of zirconium atoms of a crosslinking bisindenyl zirconium complex (B).

As a polymerization method, Preferably, it is a continuous polymerization method in which the particle | grains of an ethylene-alpha-olefin type copolymer are formed, for example, it is continuous gas phase superposition | polymerization, continuous slurry polymerization, continuous bulk polymerization, Preferably it is continuous gas phase superposition | polymerization. As a gas phase polymerization reaction apparatus, it is the apparatus which has a fluidized bed type reaction tank normally, Preferably it is an apparatus which has a fluidized bed type reaction tank which has an enlarged part. The stirring blade may be provided in the reaction tank.

As a method of supplying each component of the catalyst for metallocene olefin polymerization used for manufacture of the ethylene- alpha-olefin type copolymer of component (i) to a reaction tank, it is normally inert gas, such as nitrogen and argon, hydrogen, ethylene The method of supplying in the absence of moisture using the etc., the method of dissolving or diluting each component in a solvent, and supplying it in the solution or slurry state is used. Each component of a catalyst may be supplied individually, and arbitrary components may be previously contacted and supplied in arbitrary order.

Moreover, it is preferable to perform prepolymerization before using this superposition | polymerization, and to use the prepolymerized prepolymerization catalyst component as a catalyst component or catalyst of this polymerization.

As polymerization temperature, it is normally below the temperature which an ethylene-alpha-olefin type copolymer melt | dissolves, Preferably it is 0-150 degreeC, More preferably, it is 30-100 degreeC.

Moreover, you may add hydrogen as a molecular weight modifier for the purpose of adjusting melt fluidity of a copolymer. The inert gas may coexist in the mixed gas.

The ethylene-unsaturated ester copolymer of component (ii) is an air having monomer units based on at least one unsaturated ester selected from carboxylic acid vinyl esters and unsaturated carboxylic acid alkyl esters and monomer units based on ethylene. It is coalescing. Vinyl acetate, vinyl propionate, etc. are mentioned as this carboxylic acid vinyl ester, Moreover, as the unsaturated carboxylic acid alkyl ester, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate Alkyl acrylates such as t-butyl acrylate and isobutyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate and t-methacrylate Methacrylic acid alkyl esters, such as butyl and isobutyl methacrylate, etc. are mentioned.

As the ethylenically unsaturated ester copolymer of component (ii), preferably, an ethylene-vinyl acetate copolymer, an ethylene-methyl methacrylate copolymer, an ethylene-methyl acrylate copolymer, or an ethylene-ethyl acrylate copolymer are used. .

The melt flow rate (MFR) of the ethylene-unsaturated ester copolymer of component (ii) is usually in the range of 0.1 to 1000 g / 10 minutes, and can be appropriately selected according to the purpose. The MFR is preferably 100 g / 10 minutes or less, more preferably 50 g / 10 minutes or less, still more preferably 20 g / 10 minutes or less, and most preferably 10 g / 10 minutes from the viewpoint of increasing the strength of the pressurized foamed molded article obtained. It is as follows. In addition, from the viewpoint of increasing the resilience, the content is preferably 20 g / 10 minutes or less, more preferably 5 g / 10 minutes or less, and more preferably 4 g / 10 minutes or less.

Moreover, from a viewpoint of improving the interlayer adhesiveness of the pressurized foam molded object obtained, Preferably it is 0.2 g / 10 minutes or more, More preferably, it is 0.7 g / 10 minutes or more. Moreover, when obtaining the foamed molded object of a high foaming ratio, 4 g / 10min or more is preferable, 5g / 10min or more is more preferable, 6g / 10min or more is more preferable.

Therefore, the MFR of the ethylene-unsaturated ester copolymer of component (ii) is preferably in the range of 4 to 100 g / 10 minutes in order to obtain a high foam strength and a pressurized foamed molded article having a high foaming ratio.

Moreover, in order to obtain a pressurized foamed molded article having high foam strength and high resilience, the MFR is preferably in the range of 0.2 to 20 g / 10 minutes. Therefore, what is necessary is just to select from the said range suitably according to the objective. Moreover, the MFR is the value measured by the A method on condition of the temperature of 190 degreeC, and the load of 21.18N according to JISK7210-1995.

In the ethylene-unsaturated ester copolymer of component (ii), the total content of monomer units based on carboxylic acid vinyl esters and monomer units based on unsaturated carboxylic acid alkyl esters is determined by the total monomer units in the copolymer. The content is 100% by weight, usually 2 to 50% by weight, preferably 5 to 45% by weight. From the viewpoint of increasing the interlayer adhesion, the content is preferably 5% by weight or more, more preferably 10% by weight or more, and still more preferably 15% by weight or more. When content exceeds 50 weight%, the intensity | strength of a pressurized foam molded object may fall. More preferably, it is 40 weight% or less, More preferably, it is 35 weight% or less. The content is measured by a well-known method. For example, content of the monomeric unit based on vinyl acetate is measured according to JISK6730-1995.

The ethylene-unsaturated ester copolymer of component (ii) is produced by a known polymerization method using a known catalyst for olefin polymerization. For example, the block polymerization method using a radical initiator, the solution polymerization method, etc. are mentioned.

The resin composition of this invention is a resin composition containing component (i) and component (ii), making the total amount of component (i) and component (ii) 100 weight%, and content of component (i) is 99- It is 30 weight%, and content of component (ii) is 1 to 70 weight%. When content of a component (i) is less than 30 weight%, the balance of the light weight and rigidity of a pressurized foam molded object may fall. Preferably, content of component (i) is 40 weight% or more, More preferably, it is 50 weight% or more, More preferably, it is 60 weight% or more, Most preferably, it is 70 weight% or more. On the other hand, when content of a component (i) exceeds 99 weight%, the interlayer adhesiveness of a laminated body may fall. Preferably, the content of component (i) is 98% by weight or less, more preferably, the content of component (i) is 95% by weight or less, and the content of component (ii) is 5% by weight or more, even more preferred. Preferably, the content of component (i) is 90% by weight or less. Moreover, it is preferable that it is 70 weight% or less, and, as for content of a component (vi) from a viewpoint of raising the resilience of a pressurized foam molding, it is more preferable that it is 65 weight% or less.

In the resin composition of this invention, the total content of the monomeric unit based on the carboxylic acid vinyl ester of the component (ii), and the monomeric unit based on the unsaturated carboxylic acid alkyl ester is made up of the component (i) and the component (ii). It is preferable that it is 1 to 15 weight% from a viewpoint of making the total amount 100 weight%, and improve the interlayer adhesiveness of a laminated body, It is more preferable that it is 10 weight% or less from a viewpoint of raising the intensity | strength of a pressurized foam molding more, Furthermore, lamination It is more preferable that it is 2 weight% or more from a viewpoint of raising the interlayer adhesiveness of a sieve more.

Moreover, from the viewpoint of improving the interlayer adhesiveness of the obtained pressurized foamed molded article, the blending amount of the component (ii) when the MFR of the component (ii) to be used is small is the blending amount of the component (ii) when the MFR of the component (ii) is large. It is preferable to make more as compared with. That is, it is preferable that content of the component (ii) in the MFR of the component (ii) and the resin composition (but the total amount of the component (i) and the component (ii) is 100% by weight) satisfies the following formula (1). And it is more preferable to satisfy following formula (2).

log (M) ≥-0.02 × W + 0.48 (1)

log (M) ≥-0.02 × W + 0.85 (2)

M: MFR of component (ii) in g / 10 min

W: Content of component (ii) (unit: wt%)

In the present invention, in order to provide a pressurized foamed molded article having a particularly high light weight, high strength and high foaming ratio, and to obtain a laminate having good interlayer adhesion, preferred resin compositions are as follows.

The following component (i) and (ii) are contained, the total amount of component (i) and (ii) is 100 weight%, content of component (i) is 98-50 weight%, and content of component (ii) 2-50% by weight of the resin composition.

(Iii) an ethylene- having a monomer unit based on ethylene and a monomer unit based on an α-olefin having 3 to 20 carbon atoms, having a melt flow rate of 0.01 to 5 g / 10 minutes and an activation energy of a flow of 40 kJ / mol or more; α-olefin copolymer.

(Ii) a monomeric unit based on at least one unsaturated ester selected from a carboxylic acid vinyl ester and an unsaturated carboxylic acid alkyl ester and a monomeric unit based on ethylene, and the content of the monomeric unit based on the unsaturated ester An ethylene-unsaturated ester copolymer having 5 to 45% by weight and a melt flow rate of 4 to 100 g / 10 minutes.

In the resin composition of this invention, if necessary, metal oxides, such as a crosslinking adjuvant, a heat stabilizer, a weathering agent, a lubricating agent, an antistatic agent, a filler, and a pigment (zinc oxide, titanium oxide, calcium oxide, magnesium oxide, silicon oxide: magnesium carbonate) And various additives such as carbonates such as calcium carbonate, fiber materials such as pulp), and the like, and resins and rubber components such as high pressure low density polyethylene, high density polyethylene, polypropylene and polybutene may be blended as necessary. .

The resin composition of this invention is used suitably for manufacture of a pressurized foam molding. A well-known pressure foam molding method is employ | adopted as a manufacturing method of the pressure foam molding which uses this resin composition. For example, the composition obtained by melt-mixing the component (iii), the component (ii), and the blowing agent at a temperature at which the blowing agent is not decomposed by a mixing roll, a kneader, an extruder or the like is filled into the mold by an injection molding machine, and pressurized ( Foaming in a pressurized) and heated state, followed by cooling to take out the pressurized foamed molded product, the composition obtained by melting and mixing the composition, which is melted and mixed into a mold, and foamed in a pressurized (heated) and heated state by a press press or the like, and then cooled to pressurized foamed molded body The method of taking out it is mentioned.

In manufacture of a pressurized foam molded object, the pressurized foam molded object obtained by the said method may be cut | disconnected to a desired shape, the member obtained by cutting | disconnection may be heat-molded again, and buffing process may be performed.

As a blowing agent which can be used by this invention, the thermal decomposition type foaming agent which has the decomposition temperature more than the melting temperature of the said copolymer is mentioned. For example, azodicarbonamide, azodicarboxylic acid barium, azobisbutylnitrile, nitrodiguanidine, N, N-dinitrosopentamethylenetetramine, N, N'-dimethyl-N, N'-di Nitrosoterephthalamide, P-toluenesulfonylhydrazide, P, P'-oxybis (benzenesulfonylhydrazide) azobisisobutyronitrile, P, P'-oxybisbenzenesulfonyl semicarbazide, 5 -Phenyltetrazole, trihydrazinotriazine, hydrazodicarbonamide, etc. are mentioned, This is used 1 type or in combination of 2 or more types.

Among these, azodicarbonamide or sodium hydrogencarbonate is preferable. In addition, the compounding ratio of a foaming agent makes the total amount of component (i) and component (ii) 100 weight part, and is 1-50 weight part normally, Preferably it is 1-15 weight part.

You may mix | blend a foaming adjuvant with the composition obtained by said melt-mixing as needed. As the foaming aid, a compound containing urea as a main component; Metal oxides such as zinc oxide and lead oxide; Higher fatty acids such as salicylic acid and stearic acid; The metal compound of the higher fatty acid, etc. are mentioned. The usage-amount of foaming adjuvant makes the sum total of a foaming agent and foaming adjuvant 100 weight%, Preferably it is 0.1-30 weight%, More preferably, it is 1-20 weight%.

Moreover, you may mix | blend a crosslinking agent with the composition obtained by said melt-mixing as needed, and heat-crosslink and foam the composition which mix | blended this crosslinking agent, and it is good also as a crosslinking pressure foamed molded object. As the crosslinking agent, an organic peroxide having a decomposition temperature above the flow start temperature of the copolymer is preferably used. For example, dicumyl peroxide, 1,1-di tert-butylperoxy-3,3,5-trimethyl Cyclohexane, 2,5-dimethyl-2,5-di tert-butylperoxyhexane, 2,5-dimethyl-2,5-di tert-butylperoxyhexine, α, α-di tert-butylperoxyiso Propylbenzene, tert-butyl peroxy ketone, tert-butyl peroxy benzoate, etc. are mentioned. Moreover, when using the pressurized foamed molded object of this invention for a sole or a sole member, it is preferable to make a pressurized foamed molded object into a crosslinked pressurized foamed molded object.

In this invention, a pressurized foam can be obtained by said method, and foaming magnification is although it does not specifically limit, Preferably it is about 3 to 16 times, More preferably, it is about 5 to 13 times.

The laminated body of this invention is a laminated body formed by laminating | stacking the layer which consists of foam layers formed by pressure-foaming and molding the resin composition of this invention, and materials other than ethylene-type resin.

Examples of the material to be laminated in the pressure foam molding include other ethylene resins such as vinyl chloride resin material, styrene copolymer rubber material, and olefin copolymer rubber material (ethylene copolymer rubber material, propylene copolymer rubber material, etc.). At least 1 sort (s) of material is used from leather, cloth materials, such as a material, a natural leather material, an artificial leather material, and a cloth material.

As a manufacturing method of the laminated body of this invention, the pressurized foamed molded object formed by pressure-foaming the resin composition of this invention is shape | molded by the above-mentioned method, and the ratio which shape | molded the pressurized foamed molded object separately, then, is formed, for example. The method of joining the molded object which consists of ethylene resin materials with a thermal bonding or a chemical adhesive etc. is mentioned. A well-known thing can be used as this chemical adhesive agent. Especially, a urethane type chemical adhesive, a chloroprene type chemical adhesive, etc. are preferable. At the time of bonding with these chemical adhesives, an overcoating agent called a primer may be applied in advance.

The pressurized foamed molded article of the present invention is excellent in the balance between light weight and rigidity. For example, the pressurized foamed molded article of the present invention is excellent in light weight compared to the pressurized foamed molding made of a conventional ethylene vinyl acetate copolymer having the same degree of rigidity, and a conventional ethylene vinyl acetate having the same degree of lightness. It is excellent in rigidity as compared with pressure-foaming molding made of a copolymer. Moreover, the pressurized foamed molded article of the present invention has a good resilience and excellent strength in the above-mentioned preferred composition range. Therefore, for example, the pressurized foam molded article of the present invention is preferably used for a sole or a sole member. Moreover, since the adhesive foam with a non-ethylene resin material is also favorable, the pressurized foam molding of this invention is used by laminating | stacking with the various materials mentioned above. For example, the pressure-foaming molded article of the present invention is preferably used as an upper window (mid-sole), and the upper window is laminated with a lower window (outer-sol) made of a non-ethylene-based resin material so that the sole or sole member is laminated. Used as Moreover, the laminated body of this invention is used also for various uses, such as building materials, such as a heat insulating material and a cushioning material, in addition to a sole.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

[I] Property Measurement Method

(1) Melt flow rate (MFR, unit: g / 10 min)

According to JIS K7210-1995, it measured by the A method on condition of the temperature of 190 degreeC, and the load of 21.18N.

(2) Density (unit: ㎏ / ㎡)

After annealing as described in JIS K6760-1995, it was measured by the underwater substitution method described in JIS K7112-1980.

(3) Activation energy of flow (Ea, unit: kJ / mol)

Using a viscoelasticity measuring device (Rheometrics Mechanical Spectrometer RMS-800 manufactured by Rheometrics), the dynamic viscosity at angular temperature, 130 ° C, 170 ° C, and 190 ° C was measured under the following measurement conditions, and the resulting dynamic viscosity- From the angular velocity curve, the activation energy (Ea) was determined using the calculation software Rhios V.4.4.4 manufactured by Rheometrics.

<Measurement Conditions>

Geometry: Parallel Plates

Plate diameter: 25 mm

Plate spacing: 1.5 to 2 mm

Strain: 5%

Angular frequency: 0.1 to 100 rad / sec

Measuring atmosphere: under nitrogen

(4) Vinyl acetate unit amount (unit: weight%)

It measured according to JISK6730-1995.

(5) Density of foam molded product (unit: kg / m 2)

It measured according to ASTM-D297. The smaller this value, the better the light weight.

(6) Hardness of foam molded body (unit: none)

According to ASTM-D2240, it measured with the C method hardness tester. The larger this value, the better the rigidity.

(7) Resilience modulus of foam molded body (unit:%)

An iron sphere is freely dropped from the surface of the secondary molded body to the surface of the secondary molded body from a height of 15 cm (L ₀ ) at the surface of the secondary molded body, and the height L which the steel sphere protrudes from the surface of the secondary molded body is measured. The resilience modulus (unit:%) was calculated. The rebound elasticity was determined as follows based on the value of the rebound elastic modulus.

Resilience modulus = L / L ₀ × 100

L: Height in which the steel sphere protruded from the surface of the secondary molded body (unit: cm)

L ₀ : Falling height of the steel sphere (Unit: cm)

[Judgment]

(Circle): A resilience modulus is 40% or more.

(Triangle | delta): A resilience modulus is less than 40%.

(8) strength of foam molded body (unit: kg / cm)

According to ASTM-D642, the tear strength of the foamed molded article was measured. Specifically, the foamed molded body was sliced to a thickness of 10 mm, and then punched into the shape of No. 3 dumbbell to prepare a test piece. The test piece was pulled at a speed of 500 mm / min, and the maximum load F (kg) when the test piece was broken was divided by 1 cm in thickness of the sample piece to determine the tear strength.

(9) interlayer adhesion of laminate

From the secondary molded body, a test piece having a length of 10 cm x 2 mm x 1 cm in thickness is cut out so that the surface of the secondary molded body is one side of the test piece with a length of 10 cm x 2 mm, and the length 10 cm x 2 mm. A primer (GE-320A manufactured by Taiwan, Taiwan) was applied to only 3 cm of the cotton in the longitudinal direction, and dried at 60 ° C. for 5 minutes. Next, a liquid mixture of an adhesive ("GE-420" manufactured by the company) and a curing agent ("348" manufactured by the company. 4 wt% of the adhesive) is applied, and a rubber sheet (primer (GE-310A manufactured by Taiwan and Taiwan) is applied. ), And then dried, the adhesive ("GE-420" manufactured by the same company) and the curing agent (approximately "348" manufactured by the same company) are bonded to each other and pressed and dried at 60 ° C for 5 minutes, thereby foaming. The laminated body which has a layer and a rubber layer was obtained. The adhesive strength of the foam layer and the rubber layer was measured by peeling the foam layer and the rubber layer of the multilayer laminate at a peel rate of 50 mm / min using a 180 degree peel tester. Interlayer adhesion was evaluated by the following criterion 1 or 2 according to the adhesive strength.

Judgment standard 1

(Double-circle): Adhesive strength is 2.5 kg / cm or more in width.

(Circle): Adhesive strength is more than 2 kg / cm width and less than 2.5 kg / cm width.

X: The adhesive strength is less than 2 kg / cm width.

Judgment standard 2

(Double-circle): Adhesive strength is 3 kg / cm or more in width.

(Circle): Adhesive strength is 2 kg / cm width or more and less than 3 kg / cm width.

X: The adhesive strength is less than 2 kg / cm width.

Example 1

(1) Preparation of promoter catalyst

A solid product (hereinafter referred to as cocatalyst carrier (A)) was prepared in the same manner as component (A) of Examples 10 (1) and (2) of JP-A-2003-171415.

(2) prepolymerization

The autoclave was heated to 30 degreeC after putting 0.7 kg of said promoters (A) and 80 liters of butanes in the autoclave equipped with the 210 liter liter stirrer which carried out the nitrogen substitution previously. After ethylene was added at a gaseous pressure in the autoclave for 0.21 MPa minutes, and the system was stabilized, 70 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide was added to initiate polymerization. While heating up at 45 degreeC, the prepolymerization of a total of 4 hours was performed at 49 degreeC, supplying ethylene and hydrogen continuously. After completion of the polymerization, ethylene, butane, hydrogen gas and the like were purged, and the remaining solid was vacuum dried at room temperature to obtain a prepolymerization catalyst component in which 14 g of ethylene homopolymer was prepolymerized per 1 g of the cocatalyst carrier (A).

(3) continuous gas phase polymerization

Using said prepolymerization catalyst component, copolymerization of ethylene and 1-hexene was performed by a continuous fluidized-phase gas phase polymerization apparatus. The polymerization conditions include a temperature of 75 ° C., a total pressure of 2 MPa, a hydrogen mole ratio of 0.31% to ethylene, a 1-hexene mole ratio to 1.2% of ethylene, and ethylene, 1-hexene, hydrogen to maintain a constant gas composition during polymerization. It was fed continuously. The prepolymerization catalyst component and triisobutylaluminum were continuously fed at a constant rate so as to maintain the total powder weight of the fluidized bed at 80 kg and to have an average polymerization time of 4 hr. By polymerization, a powder of ethylene-1-hexene copolymer (hereinafter referred to as PE (1)) was obtained at a production efficiency of 22 kg / hr.

(4) Assembly of Ethylene-1-hexene Copolymer Powder

The powder of PE (1) obtained above was subjected to a feed rate of 50 kg / hr, a screw speed of 450 rpm, a gate opening of 50%, a suction pressure of 0.1 MPa, and a resin temperature of 200 to 215 using an LCM50 extruder manufactured by Kobe Steel Co., Ltd. The pellet of PE (1) was obtained by granulating on condition of ° C. The MFR of PE (1) was 0.5 g / 10 min, the density was 912 kg / m 3 and the activation energy of the flow was 72.9 kJ / mol.

(5) pressure foam molding

60 parts by weight of PE (1) and an ethylene-vinyl acetate copolymer (Evatate K2010 manufactured by Sumitomo Chemical Co., Ltd. [MFR = 3 g / 10 min, density = 940 kg / m 3, vinyl acetate unit amount = 25 wt%]; The resin composition was obtained by melt-kneading 40 weight part of EVA (1) and 40 weight part using the single screw kneading machine on the conditions of the temperature of 150 degreeC, and the screw rotation speed of 80 rpm. Next, 100 parts by weight of the resin composition, 10 parts by weight of heavy calcium carbonate, 0.5 part by weight of stearic acid, 1.5 parts by weight of zinc oxide, 3.5 parts by weight of a chemical blowing agent, 1.0 part by weight of dicumyl peroxide, and a roll kneader It knead | mixed on the conditions of roll temperature of 120 degreeC, and kneading time for 5 minutes using it, and obtained the resin composition. The resin composition was filled into a 22.8 cm x 15 cm x 1.2 cm mold, and the primary foamed molded article was obtained by pressure foaming under a condition of a pressure of 150 kg / cm 2 for a temperature of 160 ° C. for 11 minutes. Subsequently, the obtained primary foam sliced to a thickness of 1.0 cm was filled into a mold having a size of 26 cm x 18 cm x 1.0 cm, heated and pressed for 210 seconds under conditions of a temperature of 150 ° C and a pressure of 150 kg / cm 2, followed by cooling for 600 seconds. A tea molded body was obtained. Table 1 shows the results of evaluating the physical properties of the obtained secondary molded product. Moreover, the laminated body was produced by the method as described in (9) Interlayer adhesiveness of laminated body, and interlayer adhesiveness was measured. The evaluation results are shown in Table 1.

Example 2

(1) Preparation of promoter catalyst

A solid product (hereinafter referred to as cocatalyst carrier (A)) was prepared in the same manner as component (A) of Examples 10 (1) and (2) of JP-A-2003-171415.

(2) prepolymerization

Into an autoclave equipped with a nitrogen-containing 210-liter stirrer previously substituted with nitrogen, 0.6 liters of the cocatalyst carrier (A), 80 liters of butane, 0.02 kilograms of 1-butene and 3 liters of hydrogen at room temperature and atmospheric pressure were added. The clave was raised to 30 ° C. In addition, ethylene was added at a gaseous pressure in the autoclave for 0.03 MPa minutes, and after the system was stabilized, 216 mmol of triisobutylaluminum and 70 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide were added to initiate polymerization. It was. While heating up at 50 degreeC, the prepolymerization of a total of 4 hours was performed at 50 degreeC, supplying ethylene and hydrogen continuously. After completion of the polymerization, ethylene, butane, hydrogen gas and the like are purged, and the remaining solid is vacuum dried at room temperature to prepare a prepolymerization catalyst component in which 14 g of ethylene-1-butene copolymer is prepolymerized per 1 g of the promoter (A). Got it.

(3) continuous gas phase polymerization

Using said prepolymerization catalyst component, copolymerization of ethylene and 1-hexene was performed by a continuous fluidized-phase gas phase polymerization apparatus. The polymerization conditions were a temperature of 75 ° C., a total pressure of 2 MPa, a hydrogen mole ratio of 0.77% to ethylene, a 1-hexene mole ratio to ethylene of 1.98%, and ethylene, 1-hexene, and hydrogen to maintain a constant gas composition during polymerization. It was fed continuously. The prepolymerization catalyst component and triisobutylaluminum were continuously fed at a constant rate so as to maintain the total powder weight of the fluidized bed at 80 kg and to have an average polymerization time of 4 hr. By polymerization, a powder of ethylene-1-hexene copolymer (hereinafter referred to as PE (1)) was obtained at a production efficiency of 22 kg / hr.

(4) Assembly of Ethylene-1-hexene Copolymer Powder

The powder of PE (1) obtained above was subjected to a feed rate of 50 kg / hr, a screw speed of 450 rpm, a gate opening of 50%, a suction pressure of 0.1 MPa, and a resin temperature of 200 to 215 using an LCM50 extruder manufactured by Kobe Steel Co., Ltd. The pellet of PE (1) was obtained by granulating on condition of ° C. The MFR of PE (1) was 0.5 g / 10 min, the density was 912 kg / m 3, and the activation energy of the flow was 73 kJ / mol.

(5) pressure foam molding

PE (1) 80 parts by weight and an ethylene-vinyl acetate copolymer (Smitate KA-31 manufactured by Sumitomo Chemical Co., Ltd. [MFR = 7 g / 10 min, density = 940 kg / m 3, vinyl acetate unit weight = 28 wt%]; Hereinafter, 20 weight part of EVA (1) is used, and the resin composition was obtained by melt-kneading on condition of the temperature of 150 degreeC and a screw speed of 80 rpm using a uniaxial kneading machine. Next, 100 parts by weight of the resin composition, 10 parts by weight of heavy calcium carbonate, 0.5 part by weight of stearic acid, 1.5 parts by weight of zinc oxide, 3.5 parts by weight of a chemical blowing agent, 1.0 part by weight of dicumyl peroxide, and a roll kneader It knead | mixed on the conditions of roll temperature of 120 degreeC, and kneading time for 5 minutes using it, and obtained the resin composition. The resin composition was filled into the mold of 22.8 cm x 15 cm x 1.2 cm, and the primary foamed molded product was obtained by pressure-foaming on the conditions of the pressure of 150 kg / cm <2> for the temperature of 160 degreeC, and 11 hours. Subsequently, the obtained primary foam sliced to 1 cm in thickness was filled into a 26 cm x 18 cm x 1.0 cm mold, heated for 210 seconds under conditions of a temperature of 150 ° C and a pressure of 150 kg / cm 2, and then cooled for 600 seconds. A tea molded body was obtained. Table 1 shows the results of evaluating the physical properties of the obtained secondary molded product. Moreover, the laminated body was produced by the method as described in (9) Interlayer adhesiveness of laminated body, and interlayer adhesiveness was measured. The evaluation results are shown in Table 1.

Example 3

80 parts by weight of PE (1) and an ethylene-vinyl acetate copolymer (Cosmosen H2181 manufactured by The Polyolefin Co., Ltd. [MFR = 2 g / 10 min, density = 940 kg / m 3, vinyl acetate unit amount = 18 wt%]] The resin composition was obtained by melt-kneading 20 weight part of EVA (2) parts below) on the conditions of the temperature of 150 degreeC and a screw rotation speed of 80 rpm using a uniaxial kneading machine. Next, 100 parts by weight of the resin composition, 10 parts by weight of heavy calcium carbonate, 0.5 part by weight of stearic acid, 1.5 parts by weight of zinc oxide, 3.5 parts by weight of a chemical blowing agent, 1.0 part by weight of dicumyl peroxide, and a roll kneader It knead | mixed on the conditions of roll temperature of 120 degreeC, and kneading time for 5 minutes using it, and obtained the resin composition. The resin composition was filled into the mold of 22.8 cm x 15 cm x 1.2 cm, and the primary foamed molded product was obtained by pressure-foaming on the conditions of the pressure of 150 kg / cm <2> for the temperature of 160 degreeC, and 11 hours. Subsequently, the obtained primary foam was sliced to a thickness of 1.0 cm into a mold having a size of 26 cm x 18 cm x 1.0 cm, heated and pressed for 210 seconds under conditions of a temperature of 150 ° C and a pressure of 150 kg / cm 2, followed by cooling for 600 seconds. A tea molded body was obtained. Table 1 shows the results of evaluating the physical properties of the obtained secondary molded product. Moreover, the laminated body was produced by the method as described in (9) Interlayer adhesiveness of laminated body, and interlayer adhesiveness was measured. The evaluation results are shown in Table 1.

Comparative Example 1

Ethylene-vinyl acetate copolymer (Cosmosen H2181 manufactured by The Polyolefin Co., Ltd. [MFR = 2 g / 10 min, density = 940 kg / m 3, vinyl acetate unit weight = 18 wt%]; hereafter referred to as EVA (3). 100 parts by weight, 10 parts by weight of heavy calcium carbonate, 0.5 parts by weight of stearic acid, 1.5 parts by weight of zinc oxide, 3.0 parts by weight of a chemical blowing agent, and 0.7 parts by weight of dicumyl peroxide using a roll kneader It knead | mixed on 120 degreeC and the conditions of kneading time 5 minutes, and obtained the resin composition. The resin composition was filled into the mold of 22.8 cm x 15 cm x 1.2 cm, and the primary foamed molded product was obtained by pressure-foaming on the conditions of the pressure of 150 kg / cm <2> for the temperature of 160 degreeC, and 11 hours. Subsequently, the obtained primary foam was sliced to a thickness of 1.0 cm into a mold having a size of 26 cm x 18 cm x 1.0 cm, heated and pressed for 210 seconds under conditions of a temperature of 150 ° C and a pressure of 150 kg / cm 2, followed by cooling for 600 seconds. A tea molded body was obtained. Table 1 shows the results of evaluating the physical properties of the obtained secondary molded product. Moreover, the laminated body was produced by the method as described in (9) Interlayer adhesiveness of laminated body, and interlayer adhesiveness was measured. The evaluation results are shown in Table 1.

Item unit Example 1 Example 2 Example 3 Comparative Example 1 Ethylene-α-olefin Copolymer PE (1) PE (2) PE (1) - content weight% 60 80 80 - MFR g / 10 min 0.5 0.5 0.5 - density ㎏ / ㎥ 912 912 912 - Activation energy of flow kJ / mol 73 73 73 - Ethylene-vinyl acetate
Copolymer EVA (1) EVA (2) EVA (3) EVA (3) content weight% 40 20 20 100 MFR g / 10 min 3 7 2 2 density ㎏ / ㎥ 940 940 940 940 Foam molding density ㎏ / ㎥ 193 190 160 211 Hardness - 55 55 55 55 burglar Kg / cm 16.3 18.9 - 14.2 Laminate
Interlayer adhesion - ◎ ^{* 1}
○ ^{* 2} ◎ ^{* 1}
◎ ^{* 2} ○ ^{* 1}
○ ^{* 2} ◎ ^{* 1}
○ ^{* 2} Resilience ○ ○ △ ○ Note: ^* 1: Judgment Criteria 1 ^* 2: Judgment Criteria 2

This invention provides the resin composition which provides the pressurized foamed molded object which is excellent in the balance of light weight and rigidity, the pressurized foamed molded object, and the laminated body which laminated | stacked the layer which consists of a layer different from the layer of this pressurized foamed molded object and this foamed layer, In addition to the above, it is possible to provide a laminate excellent in interlayer adhesion, including a resin composition for providing a high-strength pressurized foamed molded article, a foamed molded article thereof, and a layer of the pressurized foamed molded article.

Claims (10)

It contains following component (iii) and (ii), making the total amount of component (iii) and (ii) 100 weight%, content of component (iii) is 99-30 weight%, and content of component (ii) Sole containing a pressure-foaming molded article obtained by pressure-foaming the resin composition of 1 to 70% by weight: (Iii) an ethylene- having a monomer unit based on ethylene and a monomer unit based on an α-olefin having 3 to 20 carbon atoms, having a melt flow rate of 0.01 to 5 g / 10 minutes and an activation energy of a flow of 30 kJ / mol or more; α-olefin copolymer, (Ii) An ethylene-unsaturated ester copolymer having monomer units based on at least one unsaturated ester selected from carboxylic acid vinyl esters and unsaturated carboxylic acid alkyl esters and monomer units based on ethylene. The sole according to claim 1, wherein the activation energy of the flow of the ethylene-α-olefin copolymer (i) is 40 kJ / mol or more. The sole of Claim 1 whose content of the monomeric unit based on the unsaturated ester of component (ii) is 5-45 weight%. The said resin composition contains the following component (i) and (ii), makes the total amount of component (i) and (ii) 100 weight%, and content of component (i) is 98-. Soles having 50% by weight and a content of component (ii) of 2-50% by weight: (Iii) an ethylene- having a monomer unit based on ethylene and a monomer unit based on an α-olefin having 3 to 20 carbon atoms, having a melt flow rate of 0.01 to 5 g / 10 minutes and an activation energy of a flow of 40 kJ / mol or more; α-olefin copolymer, (Ii) a monomeric unit based on at least one unsaturated ester selected from a carboxylic acid vinyl ester and an unsaturated carboxylic acid alkyl ester and a monomeric unit based on ethylene, and the content of the monomeric unit based on the unsaturated ester An ethylene-unsaturated ester copolymer having 5 to 45% by weight and a melt flow rate of 4 to 100 g / 10 minutes. It contains following component (iii) and (ii), making the total amount of component (iii) and (ii) 100 weight%, content of component (iii) is 99-30 weight%, and content of component (ii) Laminated body formed by laminating | stacking the foam layer of the pressurized foamed molded object obtained by pressure-foaming this 1-70 weight% resin composition, and the layer which consists of materials other than ethylene resin: (Iii) a monomer unit based on ethylene and a monomer unit based on an α-olefin having 3 to 20 carbon atoms, a melt flow rate of 0.01 to 5 g / 10 minutes, and an activation energy of the flow of 30 kJ; Ethylene-α-olefin-based copolymer that is / mol or more, (Ii) An ethylene-unsaturated ester copolymer having monomer units based on at least one unsaturated ester selected from carboxylic acid vinyl esters and unsaturated carboxylic acid alkyl esters and monomer units based on ethylene. The laminated body of Claim 5 whose activation energy of the flow of an ethylene-alpha-olefin type copolymer (i) is 40 kJ / mol or more. The laminated body of Claim 5 whose content of the monomeric unit based on the unsaturated ester of component (ii) is 5-45 weight%. The said resin composition contains following component (i) and (ii), makes the total amount of component (i) and (ii) 100 weight%, and content of component (i) is 98-. 50 weight% and laminated body whose content of component (ii) is 2-50 weight%: (Iii) an ethylene- having a monomer unit based on ethylene and a monomer unit based on an α-olefin having 3 to 20 carbon atoms, having a melt flow rate of 0.01 to 5 g / 10 minutes and an activation energy of a flow of 40 kJ / mol or more; α-olefin copolymer, (Ii) a monomeric unit based on at least one unsaturated ester selected from a carboxylic acid vinyl ester and an unsaturated carboxylic acid alkyl ester and a monomeric unit based on ethylene, and the content of the monomeric unit based on the unsaturated ester An ethylene-unsaturated ester copolymer having 5 to 45% by weight and a melt flow rate of 4 to 100 g / 10 minutes. A group according to claim 5, wherein the layer made of materials other than ethylene-based resin is made of a vinyl chloride resin material, a styrene copolymer rubber material, an olefin copolymer rubber material, a natural leather material, an artificial leather material, and a cloth material. A laminate, which is a layer containing at least one material selected from. A sole containing the laminate according to any one of claims 5 to 9.