JPH04197625A - Polyolefin resin foam laminated matter - Google Patents

Abstract

PURPOSE:To improve adhesion or printing properties or metallizing properties by making the subject matter superior in antistatic properties and free from generation of bleeding or blocking, by providing a resin layer containing polyolefin resin of an ethylene structural unit, acrylate structural unit and specific acrylamide structural unit. CONSTITUTION:Polyolefin resin containing polyolefin resin having 1000-50000 weight-average molecular weight arranged linearly and irregularly, which is comprised of a 65-99mol% ethylene structural unit represented by [CH2-CH2], a 0-15mol% acrylate structural unit represented by a formula I and a 1-35mol% acrylamide structural unit represented by a formula II is provided as resin for a resin layer. In the formula, R<1>, R<2>, R<3>, R<4>, R<5> and X represent respectively an alkyl group of 1-4C, an alkylene group of 2-8C, the alkyl group of 1-4C, the alkyl group of 1-4C, an alkyl group of 1-12C, an aryl alkyl group of 1-12C or a cycloaliphatic alkyl group of 1-12C and a halogen atom or CH3OSO3 or C2H5OSO3.

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to polyolefin resin foam laminates. More specifically, it relates to polyolefin resin foam laminates that have antistatic properties and can be suitably used as materials for household items such as bath mats, packing materials, insulation materials, and automobile interior materials. . [Prior Art] In general, foams made of polyolefin resins, particularly polyethylene resins and polypropylene resins, are highly hydrophobic and therefore generate a significant amount of static electricity, which can cause dust to adhere to the foam and static electricity. There is a problem of not giving shock to the human body due to the discharge. Therefore, in order to impart antistatic properties to foams, methods of adding anionic, cationic or amphoteric surfactants, and methods of adding anionic, cationic or amphoteric surfactants to polyolefin resin foams have been proposed.
-121717 publication and the resin described in Japanese Patent Publication No. 1. -29
The resin coating method described in Japanese Patent No. 820 has been adopted. However, in the method of adding a surfactant, since the surfactant has a relatively small molecular weight of about 500 to 600, it may volatilize during the production of the foam, or There are other problems, such as bleed-out with aging, contaminating the surface of the foam, causing blocking, deteriorating adhesion, printability, vapor deposition, and poor durability of the effect. In addition, in the method of coating with the specific resin, since none of the resins are polyolefin resins, the adhesiveness with the polyolefin resin foam is poor, and the polyolefin resin foam laminate, which is the object of the present invention, has poor adhesion. I can only do scales. Also,
Is it possible to consider adding such a resin to the foam? In this case, the problem is that the compatibility with polyolefin resins is poor, resulting in lipoids with poor transparency and poor surface properties. be. Additionally, when these resins and surfactants are included in foams, unlike sheets and films, the volume of the product increases, and as a result, unless a large amount of the resins and surfactants mentioned above are added, charging will occur. There is a problem that preventive properties are difficult to demonstrate. U Invention or problem to be solved] The present invention has been made in view of the above-mentioned prior art,
The purpose is to provide a polyolefin resin foam laminate that not only has excellent antistatic properties but also does not cause bleeding or blocking and has excellent adhesion, printability, and vapor deposition properties. It is something. [Means for Solving the Problems] The present invention comprises 65 to 99 mol% of ethylene structural units represented by the formula +CH2-CH2+, the general formula. -+CH2-CH→ (wherein R1 represents an alkyl group having 1 to 4 carbon atoms) and the general formula: (wherein R2 represents an alkyl group having 2 to 4 carbon atoms) an alkylene group, R3 and R4 are each an alkyl group having 1 to 4 carbon atoms, R5 is an alkyl group having 1 to 12 carbon atoms, an arylalkyl group having 1 to 12 carbon atoms, or an alicyclic alkyl group having 1 to 12 carbon atoms, X is a halogen atom, CH
30SO3 or C2Hs03O3) consisting of 1 to 35 mol% of acrylamide structural units arranged irregularly in a linear manner with a weight average molecular weight of 1000 to 500
The present invention relates to a polyolefin resin foam laminate characterized in that it is provided with a polyolefin resin layer containing a polyolefin resin of No. 00. [Function and Examples] As described above, the polyolefin resin foam laminate of the present invention has 65 to 99 moles of ethylene structural units represented by the formula: 10 CH2-CH2, and the general formula: ÷CH2-C11- (in the formula, R1 has 1 to 40 carbon atoms)
acrylate structure φ represented by (representing the alkyl group of R1)
position 0 to 15 mol% and general formula: (wherein, R2 is an alkylene group having 2 to 8 carbon atoms, R3 and R4 are each an alkyl group having 1 to 4 carbon atoms, R5 is an alkyl group having 1 to 12 carbon atoms, An arylalkyl group having 1 to 12 carbon atoms or an alicyclic alkyl group having 1 to 12 carbon atoms, X is a halogen atom, CH3
0SO3 or C2R503O3) consisting of 1 to 35 mol% of acrylamide structural units arranged irregularly in a linear manner and having a weight average molecular weight of 1000 to 50,000
A polyolefin resin containing a polyolefin resin is provided as a resin for the resin layer. The proportion of ethylene structural units represented by the formula: 1,000 H2-CH2÷ in the polyolefin resin is 65 to 99 mol%. When the proportion of the ethylene structural unit is less than 65 mol%, the softening point of the polyolefin resin becomes low, resulting in tackiness and stickiness, and when it exceeds 99 mol%, the polyolefin resin The antistatic property of the product becomes too small. In addition, in the present invention, the proportion of the ethylene structural unit is determined from the viewpoint of softening point and antistatic property.
It is particularly preferable that the content is 85 to 97 mol%. General formula in the polyolefin resin: 10H2-C
11-+ (in the formula, R1 is the same as above) (2) The proportion of acrylate structural units represented by C0OR is 0 to 15 mol%. If the proportion of the acrylate structural unit exceeds 15 mol%, the softening point of the polyolefin resin becomes low, resulting in tackiness or stickiness. In the present invention, when the acrylate structural unit is included, it is preferable because it imparts toughness and impact resistance.In the present invention, the proportion of the acrylate structural unit is From the point of view of balance between strength, toughness, and impact resistance, it is particularly preferably 1 to 15 mol%, particularly 3 to 7 mol%.In the acrylate structural unit, R1 has 1 to 1 carbon atoms.
4 is an alkyl group. As a specific example of such R1,
Examples include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, and 1-butyl group, and these groups may be mixed in one molecule. Note that among these groups, methyl and ethyl groups are preferred for maintaining the softening point of the polyolefin resin. General formula in the polyolefin resin. The proportion of the acrylamide structural unit represented by (wherein R2, R3, R4 and R5 are the same as above) is 1 to 35 mol%. If the proportion of the acrylamide structural unit is less than 1 mol%, the antistatic property may be reduced, and if it exceeds 35 mol%, the polyolefin resin may become hygroscopic. Become. In the present invention, the proportion of the acrylamide structural unit is particularly preferably 3 to 15 mol% from the viewpoint of balancing antistatic properties and hygroscopic properties. In the acrylamide structural unit, R2 has 2 carbon atoms.
~8 alkylene group. Specific examples of such R2 include, for example, ethylene group, propylene group, hexamethylene group, and neopentylene group, and these groups may be mixed in one molecule. Among these groups, ethylene and propylene groups are preferred from the viewpoint of ease of production and economy, and propylene groups are particularly preferred. R3 and R4 are each an alkyl group having 1 to 4 carbon atoms. Specific examples of such R3 and R4 include methyl group, ethyl group, propyl group, butyl group,
These groups may be mixed in one molecule. Among these groups, methyl and ethyl groups are preferred from the viewpoint of antistatic properties. The above R5 is an alkyl group having 1 to 12 carbon atoms, and 1 to 1 carbon atoms.
2 arylalkyl group or an alicyclic alkyl group having 1 to 12 carbon atoms. Specific examples of GagaruR5 include alkyl groups such as methyl group, ethyl group, n-propyl group, 1-propyl group, n-butyl group, 5ec-butyl group, n-octyl group, and n-lauryl group. ;benzyl group, 4-
Examples include arylalkyl groups such as methylbenzyl group, alicyclic alkyl groups such as cyclohexyl group, and methylcyclohexyl group, and these groups may be mixed in one molecule. In addition, from the viewpoint of heat resistance, R5 is preferably a linear alkyl group or an arylalkyl-class alkyl group. Particularly preferable examples of R5 include a methyl group and an ethyl group. The above X is, for example, a nitrogen atom such as Cj, Br, 1, CH30SO3 or C2HSOSO3, and these may be mixed in one molecule.
Among these, CI, CH3 are preferred from the viewpoint of antistatic properties.
0SO3 and C2 HS 0303 are preferred. The weight average molecular weight of the polyolefin resin is 100
It is 0-50000. The weight average molecular weight force・1000
If it is less than 5,000, the molecular weight becomes too small and will volatilize when heated, and if it exceeds 5,000,
The viscosity when melted becomes too high, making workability difficult. Preferably 0 weight average molecular weight is 3000 to 30000
It is. In addition, in this specification, the weight average molecular weight refers to the weight average molecular weight in terms of monodisperse polystyrene measured by gel permeation chromatography (GPC). The polyolefin resin used in the present invention is poorly soluble in ordinary gel permeable eluents such as tetrahydrofuran (TI[F) and xylene, so its weight average molecular weight cannot be easily measured or its weight average molecular weight is extremely high. high temperature GP
C method (for silk, Polymer Journal, Vol. 44, No. 2, 139-1
41 (1987)). Formula: + C) which is an intermediate of the polyolefin resin
12 -CH2→ Ethylene structural unit, general formula: CH2-C11÷ (in the formula, R1 is the same as above)
Acrylate structural unit and general formula represented by OOR1. An olefin copolymer having a weight average molecular weight of 1,000 to 50,000 and having a linear and irregularly arranged acrylamide structural unit represented by the formula (wherein R2, R3 and R4 are the same as above) can be prepared, for example, by the following method. available. First, the raw material for the olefin copolymer is not particularly limited, but it is more advantageous to use ethylene (C2H4) and an acrylate represented by the general formula CH2C)ICOORI (wherein R1 is the same as above). A (partial) hydrolyzate of a copolymer of The ratio of acrylate structural units derived from acrylate to acrylate structural units will determine the ratio of ethylene structural units, acrylate structural units and acrylamide structural units in the resulting olefin copolymer. The copolymer usually has a melt index of 5. Since it has a high molecular weight of about ~300, it is preferable to reduce the molecular weight by a degradation method that simultaneously performs hydrolysis and thermal decomposition under high temperature and pressure in the presence of water. The general formula: +CH2-CII (in the formula, R1 is the same as above) is expressed as OORI. By hydrolyzing all or part of the middle position of the acrylate structure, the formula: In order to reduce the molecular weight by thermally decomposing the copolymer and prepare a copolymer with a polymerization degree of 50 to 600, the copolymer is reacted in the presence of water. Temperature 150-500℃,
The molecules may be cut by heating at a pressure of 3 to 500 kg/cd. In the present invention, the proportion of the acrylic acid structural units can be adjusted as appropriate by adjusting the amount of water, reaction temperature, pressure, and reaction time. As a specific example of the above-mentioned degradation method, for example, JP-A-53-
The methods described in JP-A-57295, JP-A-53-65389, JP-A-H-79008, and JP-A-60-79015 are mentioned. Note that if the polyolefin resin used in the present invention is colored, it may impair its commercial value.
It is preferable to use the product of the method exemplified in Japanese Patent No. 79008. The polyolefin resin intermediate thus obtained can be used to convert the polyolefin resin used in the present invention. There are no particular limitations on the method for producing the polyolefin resin used in the present invention from the intermediate. An example will be explained below. The intermediates are, for example, benzene, toluene, xylene,
Dissolve in an inert solvent such as an aromatic or aliphatic hydrocarbon such as cyclohexanone, decane, cumene, cymene, etc., and add 100 to 15
Add 0 mol% of a dialkylamine monomer such as dialkylaminoalkylamine, and react at 130 to 220°C to convert the carboxyl group contained in the acrylic acid structural unit to a dialkylaminoalkylamide group, forming an intermediate. Thereafter, the polyolefin resin, which is a linear random copolymer used in the present invention, is changed by cationic modification with a known quaternizing agent such as an alkyl halide or a dialkyl sulfate. The polyolefin resin thus obtained exhibits excellent antistatic properties. The reason for this antistatic property is not clear, but the acrylamide structural unit contained in the polyolefin resin may absorb moisture from the air, ionize the xe, and exhibit electrical conductivity, resulting in low electrical resistance. This is thought to be due to the fact that In addition, in the present invention, since the acrylamide structural unit exhibits volatility even under high temperatures and is chemically incorporated into the polyolefin resin used in the present invention, it does not volatilize during processing. It is considered that no prosokink occurs after processing. The polyolefin resin foam laminate of the present invention is provided with a resin for a resin layer containing the above-mentioned polyolefin resin, and the resin for the resin layer may be a polyolefin resin alone or this resin and other polyolefin resins. A mixture of these is used. The other polyolefin resins include, for example, an ethylene-propylene copolymer having an ethylene content of 2 to 30% by weight, a terpolymer obtained by further copolymerizing butene-1 to the ethylene-propylene copolymer, and a high-pressure method. Low density polyethylene, linear low density polyethylene, linear very low density polyethylene, high density polyethylene, ethylene-hinyl acetate copolymer, saponified product of the above ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer,
Examples include ethylene-(meth)acrylic acid ester copolymer, ethylene-(meth)acrylic acid-maleic anhydride terpolymer, and ethylene-(meth)acrylic acid ester-maleic anhydride terpolymer. These resins may be used alone or in combination of two or more. In addition, when the above-mentioned polyolefin-based resin and the above-mentioned other polyolefin-based resin are used together, the amount of the above-mentioned polyolefin-based resin used is 0.00 parts (parts by weight, the same shall apply hereinafter) based on 100 parts (parts by weight, the same shall apply hereinafter) of the resin for the resin layer obtained. It is desirable that the amount is 1 part or more, preferably 10 parts or more, in order to impart antistatic properties. The resin composition of the polyolefin resin foam used as a base material in the present invention is not particularly limited, and may be appropriately selected and used depending on the use of the polyolefin resin foam laminate to be obtained. Examples of resins that can be used for the polyolefin resin foam include polypropylene,
Various copolymers of propylene and other olefins, such as ethylene-propylene copolymers with an ethylene content of 2 to 30% by weight and terpolymers obtained by further copolymerizing butene-1 to the ethylene-propylene copolymers. union, high-pressure process low-density polyethylene, low-pressure process high-density polyethylene, linear low-density polyethylene, linear ultra-low-density polyethylene, ethylene-vinyl acetate copolymer, saponified product of the ethylene-vinyl acetate copolymer, Ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid ester, ethylene-(meth)acrylic acid-maleic anhydride terpolymer,
Examples include ethylene-(meth)acrylic acid ester-maleic anhydride terpolymer, and these resins may be used alone or in combination of two or more. There are no particular limitations on the method for producing the polyolefin resin foam used in the present invention, and known production methods can be applied. Specific examples include, for example, a method in which a decomposable foaming agent is mixed with a foamable resin composition and introduced into an extruder, the foaming agent is decomposed and foamed, and a method in which a foamable resin composition is introduced into an extruder and then The so-called extrusion foaming method involves pressurizing an evaporative solvent into an extruder to form foam.The foamable resin composition is filled into a mold with a mixture of a decomposable blowing agent and a peroxide compound, and heated under pressure to decompose the peroxide compound. In the so-called block foaming method, the foaming resin composition is introduced into an extruder, formed into a sheet, and then irradiated with an electron beam. Alternatively, a normal pressure crosslinking and foaming method may be used, in which a peroxide compound is added to perform crosslinking, followed by heating and foaming. The expansion ratio and thickness of the polyolefin resin foam are not particularly limited and may be appropriately selected depending on the use of the resulting polyolefin resin foam laminate. In the present invention, for example, inorganic fillers such as calcium carbonate, talc, and glass single fibers, antioxidants, flame retardants, colorants,
Various auxiliary agents such as polyfunctional monomers may be included in the resin for the resin layer and the foam. Further, in the present invention, a known low molecular weight surfactant may be used in the resin for the resin layer and the foam in an amount not exceeding 30 parts per 100 parts of the polyolefin resin. If the surfactant is used in an amount not exceeding 30 parts as described above, no bleeding is observed. There is no particular limitation on the method of laminating the resin for the resin layer on the polyolefin resin foam, but examples include a method of laminating the resin for the resin layer by the itastrusion lamination method, polyolefin resin foaming, etc. A method of directly laminating resin layer resin during body manufacturing,
Specifically, a method is used in which the resin for the resin layer is compositely laminated on one or both sides of the resin in a molten state to form a foam, and then foamed, and the resin for the resin layer is heated and melted, and then melted or emulsified with a solvent. There are methods of coating the surface of the foam by a reverse roll coating method, a gravure coating method, a barcode method, and the like. The thickness of the polyolefin resin layer is preferably 1 to 150JA1 when used as a final product, and preferably 3 to 100JA1.
．． , more preferably within the range of 5 to 5. If the thickness is less than 1 um, cohesive failure will occur at the interface between the resin layer and the foam, resulting in poor adhesion and vapor deposition, and if it exceeds +50 left, The flexibility of the resin layer becomes noticeable, and phenomena such as blocking occur. The polyolefin resin foam laminate of the present invention thus obtained can be further subjected to a corona discharge treatment on at least one side to increase surface wetting tension and improve adhesion with various water-soluble coating agents. In addition, a coating agent layer is provided, and various skin materials, films, sheets, other foams, metal foils, paper, nonwoven fabrics made of natural fibers or synthetic fibers, or synthetic leather are laminated to form a composite.
These can be molded by various methods. Next, the polyolefin resin foam laminate of the present invention will be explained in more detail based on Examples, but the present invention is not limited to these Examples. Example 1 High-pressure low-density polyethylene (
Density: 0.921g/cm3, Melt index:
3.7g/10min, particle size: 32 mesh pass) 10
A mixture of 0 parts and 10 parts of azodicarbonamide as a blowing agent was used. In addition, as a resin for the resin layer, 85 mol% of ethylene structural units represented by the formula: +CH2-CH2, and the formula: +CH2-
A polyolefin resin having a weight average molecular weight of 21,000 and having a weight average molecular weight of 21,000 and consisting of 5 mol% of an acrylate structure COOC2H5 unit represented by Cll-t and IO mol% of an acrylamide structural unit represented by the formula: The one that was crushed was used. Next, two extruders are prepared, and after introducing the foamable resin composition and the resin layer resin into each,
The melted composite continuous sheet is introduced into a lamination device equipped with a nozzle composite equipment, melted and kneaded, and the thickness of the resin layer is about 500 mm, and the thickness of the foamable resin layer that becomes the foam is about 15 mm, and the width is about 500 mm. was molded. This sheet was crosslinked by irradiating the sheet with an electron beam of 5 Mrad using an electron beam irradiation machine to obtain a crosslinked foamable laminate. The obtained crosslinked foamable laminate sheet was continuously introduced into a vertical hot air foaming machine in a heating atmosphere of 230° C. 7 to obtain a foamed laminate. This foam laminate has a total thickness of 3.3 mr@
The total width was 1170 m+n, the apparent foaming ratio was 20 times, and the thickness of the resin layer was 43 mm. When the surface resistivity of the foamed laminate obtained was examined according to the method described below, it was found that it was extremely small, 3.2×1.08Ω, and had excellent antistatic properties. At the same time, the obtained foam laminate was heated at 40°C and 80% RH (
The surface of the resin layer of the foam laminate was observed after being left in an atmosphere of relative humidity for 7 days. Printed using printing ink for polypropylene, or had no printing defects due to bleed-out. Next, one side of the obtained foamed laminate was subjected to corona discharge treatment, and the surface wetting tension was increased to 45 dyne/crA or more, thereby improving the adhesion with various coating agents. In addition, a coach ink layer is provided, and various skin materials, films, sheets, other foams, metal foils, paper, nonwoven fabrics made of natural fibers or synthetic fibers, or synthetic leather are laminated to form a composite. It was possible to mold it into the desired shape using this method. (Surface resistivity) Cut the foam laminate into a piece of 10cm x locm,
℃, in a constant temperature room controlled at 60% R11.
Leave it for 8 hours and knee sink. After the knee zinc is finished, the surface resistivity δ1 is determined in the above atmosphere. Measuring instrument - A super insulating old model (VE-40 model) manufactured by Kawaguchi Electric Manufacturing Co., Ltd. connected to a normal temperature measurement box (RC-02 model).Measurement conditions: Applied voltage + 00V.The value measured with a wooden instrument is used. Incidentally, a material having the above-mentioned surface specific resistance of 1×10 13 Ω or less and the above-mentioned charge half-life of 3 minutes or less is considered to have antistatic properties. Example 2 Low density polyethylene (density:
0.923 g/crA, melt index. 1.2g/10min, particle size: 32 mesh bath) 100
10 parts of azone carbonamide as a blowing agent was added and mixed. In addition, as a resin for the resin layer, the formula: CH2-CH2-+
85 mol% of ethylene structural units represented by formula: −+−
Acrylate structure CO expressed as cH2-C11÷
A polyolefin resin having a weight average molecular weight of 30,000 and consisting of 5 mol % of OC2Hs units and LO mol % of acrylamide structural units represented by the formula: linearly irregularly arranged was used. Next, a foamed laminate was obtained in the same manner as in Example] using the foamable resin composition and the resin for the resin layer. This foam laminate has a total thickness of 1.9 mm and a total width of 117 mm.
0mm, apparent foaming ratio is 15x, resin layer thickness is 50x
It was from Canada. Next, as physical properties of the foamed laminate obtained, surface resistivity was investigated in the same manner as in Example 1, and charge half-life, bleed-out, and blocking shear force were investigated using the following methods. The results are shown in Table 1. (Half-life of charge) Using a static honest meter (manufactured by Shishido Shokai) in the same atmosphere as when measuring the surface resistivity,
A voltage of KV is applied, and the decay rate of the applied charge is determined as the half-life. (Bleed-out) Additive-free biaxially oriented polypropylene film is layered on the surface of the foam laminate and left in an atmosphere of 80% R1 at 40°C for 7 days. Inspect the presence or absence of deposits on the surface. (Blocking shear force) Two foam laminates are overlapped over a width of 3 cm and a length of 4 cm, a weight of 550 g is placed on top of the foam laminate, and heated at 40°C.
After being exposed to an atmosphere of 80% RH for 7 days, the shear peeling force of the two foams was determined using a Schopper type tensile tester. A shear peeling force of 1000g or less is considered a pass. Note that it is preferably 500 g or less. Example 3 Low density polyethylene (density
0.921 g/a+f, melt index:
13 parts of azone carbonamide and 1 part of dicumyl peroxide were added as blowing agents to 100 parts (3.2 g/l, 0 minutes). In addition, the resin for the resin layer is composed of 80 mol% of ethylene structural units represented by the formula +CH2-CH2→ and 20 mol% of acrylamide structural units represented by the formula, which are irregularly arranged in a linear manner and have a weight average molecular weight of 31. ooOO
80 parts of polyolefin resin pulverized to 32 mesh pass and low density polyethylene (density 0
．． 921 g/cm3, melt index +3.2g
/l, 0 minutes, particle size = 32 mesh pass) was used. Example 1 was obtained by decomposing and crosslinking dicumyl peroxide using the foamable resin composition obtained next and the resin for the resin layer, except that no electron beam was irradiated. A foam laminate was obtained in the same manner. This foam laminate has a total thickness of 3'03 mm and a total width of 1170 m.
m, the polishing foaming magnification is 25 times, and the thickness of the resin layer is 30ff.
It belonged to l. The physical properties of the obtained foam laminate were investigated in the same manner as in Example 2. The results are shown in Table 1. Example 4 Linear low density polyethylene (density + 0.925 g/cm, melt index: 2 g/10 min) and low density polyethylene (density: 0.925 g/cm) and low density polyethylene (density: 0.925 g/cm, melt index: 2 g/10 min) were used as foamable resin compositions.
923 z / cnt, melt index 15
g/10 minutes) mixed at a weight ratio of 30/70.
. 10 parts of azodicarbonamide as a foaming agent. In addition, as a resin for the resin layer, a linear structure consisting of 80 mol% of ethylene structural units represented by the formula ÷CH2-CHr÷, 1 mol% of acrylamide structural units represented by the formula: 80 parts of an irregularly arranged polyolefin resin having a weight average molecular weight of 27,000 and 20 parts of the same linear low density polyethylene as used in Example 3 were used. Next, a foamed laminate was obtained in the same manner as in Example 1 using the obtained foamable resin composition and the resin layer resin. This foam laminate has a total thickness of 4 parts 5 mm and a total width of 117 mm.
0mm, apparent foaming ratio is 20x, resin layer thickness is 50x
It was something like that. The physical properties of the obtained foam laminate were investigated in the same manner as in Example 2. The results are shown in Table 1. Example 5 Ethylene-propylene copolymer (ethylene content: 8% by weight, melt index'
2.3 g/10 minutes) was used in which 4 parts of azodicarbonamide was added as a blowing agent to 100 parts. In addition, as a resin for the resin layer, 88 mol% of ethylene structural units represented by the formula: +CH2-CH2 and the formula:
Acrylate structure expressed as H2-C1l÷

[10 parts of a linearly irregularly arranged polyolefin resin with a weight average molecular weight of 33,000 consisting of 3 mol % of COOC2H5 units and 9 mol % of acrylamide structural units represented by the formula were ground to 32 mesh baths. Polypropylene [Melt index 2.5 g/10 minutes, particle size 232 mesh bath]
90 parts was used. Next, a foamed laminate was obtained in the same manner as in Example 1 using the obtained foamable composition and resin for the resin layer. The resulting foam laminate has a total thickness of 4.2 mm and a total width of 1 mm.
170mm, apparent foaming ratio is 9 times, thickness of resin layer is 1
It was 50 parts m. The physical properties of the obtained foam laminate were investigated in the same manner as in Example 2. The results are shown in Table 1. [Margin below] Comparative example] Polypropylene (melt index: 2.5g/1
A resin for a resin layer was obtained by mixing 99 parts of 0 min, particle size: 232 mesh pass) and 1 part of stearic acid monoglyceride as an antistatic agent. Ethylene-propylene copolymer (ethylene content 5% by weight, melt index + 1.2g/10min) 10
A foamable composition was obtained by mixing 15 parts of azodicarbonamide and 1 part of dicumyl peroxide as foaming agents. Next, a foamed laminate was obtained in the same manner as in Example 3 using the obtained foamable composition and resin for the resin layer. The physical properties of the obtained foam laminate were investigated in the same manner as in Example 2. The results are shown in Table 2. Comparative example 2 Polypropylene (melt index 2.5g/10
minutes, particles: 32 mesh pass) 99.2 parts and formula as an antistatic agent. A resin for the resin layer was obtained by mixing 0.8 part of a hetain type amphoteric surfactant represented by: A foamable composition was prepared by mixing 100 parts of the same ethylene-propylene copolymer used in Comparative Example 1 and 2 parts of azodicarbonamide and 2 parts of divinylbenzene as foaming agents. Next, a foamed laminate was obtained in the same manner as in Example 1 using the obtained foamable composition and resin for the resin layer. The physical properties of the obtained foam laminate were investigated in the same manner as in Example 2. The results are shown in Table 2. Comparative Example 3 Linear low density polyethylene (density: 0.921.g/
cm3, melt index: 3.2g/10 minutes,
98.5 parts (particle size = 32 mesh bath) and 1.5 parts of a hetain type amphoteric surfactant represented by the formula stearic acid monoglyceride as an antistatic agent were mixed to form a resin layer. I got a resin for this. A foamable composition was prepared by mixing 100 parts of the same low-density polyethylene as used in Example 4 and 15 parts of azodicarbonamide as a foaming agent. A foam was obtained in the same manner as in Example] using the foamable composition and the resin for the resin layer. The physical properties of the obtained foam laminate were investigated in the same manner as in Example 2. The results are shown in Table 2. Comparative Example 4 95 parts of an ethylene-propylene copolymer with an ethylene content of 5% by weight (melt index: 1.2 g/10 minutes, particle size/32 mesh pass) and 1 part of dodecylhensensulfonic acid sodium and polyethylene glycol as antistatic agents. A resin for the resin layer was obtained by mixing the mixture at a weight ratio of 1. A foamable composition was prepared by mixing 100 parts of the same polypropylene used in Example 5 and 2 parts of azodicarbonamide, 1 part of dicumyl peroxide, and 2 parts of divinylbenzene as foaming agents. Next, a foamed laminate was obtained using the foamable composition and the resin for the resin layer in the same manner as in Example 1. The physical properties of the obtained foam laminate were investigated in the same manner as in Example 2. The results are shown in Table 2. Comparative Example 5 Polypropylene (melt index: 2.5g/1
0 minutes, particle size 32 mesh pass) 99.2 parts and 0.8 parts of stearylgetanolamine as an antistatic agent.
A resin for the resin layer was obtained by mixing the two parts. Also, 100 parts of the polypropylene, 2 parts of azodicarbonamide as a blowing agent, and 2 parts of divinylbenzene.
A foamable composition was obtained by mixing the two parts. Next, a foamed laminate was obtained in the same manner as in Example 1 using the obtained foamable composition and resin for the resin layer. The physical properties of the obtained foam laminate were investigated in the same manner as in Example 2. The results are shown in Table 2. [Left below] From the results shown in Table 1, the polyolefin resin foam laminate of the present invention has a surface resistivity, which is an index of antistatic property, of 1×1013Ω or less, and a charge half-life of 180 seconds or less. In addition, there was no bleed-out of the antistatic component from the resin layer of the foamed laminate, indicating that it was a foamed laminate with excellent antistatic properties without blocking. On the other hand, the foamed laminates obtained in Comparative Examples 1 to 5 were those in which a conventional relatively low molecular weight surfactant-type antistatic agent was used, and from the results shown in Table 2, it was found that If you try to satisfy the properties, it is obvious that the antistatic agent bleeds out from the foam, resulting in blocking. Example 6 The same polyolefin resin used in Example 1 was prepared, and the polyolefin resin was poured into ion-exchanged pure water heated to 60°C, stirred and dispersed at high speed with a homolyzer, and made into an emulsion at room temperature. An emulsion containing 24% by weight of the resin was obtained. Next, low density polyethylene (density: 0.923g
/ crA, melt index: 3.2g/
10 minutes), and the emulsion was roll coated onto the surface of a foam (expansion ratio: 20 times, thickness: 3 mr@) obtained by the normal pressure crosslinking foaming method, so that the thickness of the resin layer was 577 cm.
After coating to give TII, it was supplied to a hot air drying oven at 120°C, dried, and then wound up. The thickness of the resin layer after drying was 2 doors. When the surface resistivity of the foamed laminate obtained was measured in the same manner as in Example], it was found that it was extremely small, 3.2×10 8 Ω, and had excellent antistatic properties. At the same time, prepare two sheets of the obtained foam laminate, overlap the coated side and the uncoached side, and
After being placed in an atmosphere of 0° C. and 80% RH for 24 hours, it was peeled off and the surface of the foamed laminate was observed, and it was found that there was no stickiness due to bleed-out, and no blocking occurred. In addition, printing was performed on the resin layer surface of the obtained foam laminate using printing ink for polypropylene and printing ink for cellophane, and there were no printing defects due to bleed-out. Next, the resin layer surface of the obtained foam laminate was coated with a thickness of about 20 mm.
~50. Although aluminum was vapor-deposited to a certain extent, the adhesion of the vapor-deposited film was extremely good, and no whitening, peeling, or falling-off of the vapor-deposited film due to bleed-out was observed. Further, one side of the obtained foamed laminate was subjected to a corona discharge treatment, and the surface wetting tension was set to 37 dyne/cm or more, thereby improving the adhesion with various coating agents. Furthermore, by providing a coating agent layer on the resin layer and laminating it with other films or sheets, or providing a heat sealant layer, it was possible to use it as various packaging materials. Example 7 A foamable resin composition was obtained by mixing 100 parts of polypropylene (melt index, 23 g/10 minutes) with 5 parts of azonecarphonamide and 2 parts of divinylbenzene as blowing agents. The obtained foamable resin composition was introduced into an extruder heated to 170 to 180°C, and the foaming agent was melted and kneaded so as not to decompose to obtain a foaming sheet having a thickness of 2.0 mm. Furthermore, this material was crosslinked by irradiation with an electron beam of 2.88 rad, and then introduced into a silicone bath heated to 230°C and foamed to obtain a foam with a thickness of 2.5 mm and a foaming ratio of 10 times. . The same polyolefin resin used in Example 2 and an ethylene-vinyl acetate copolymer (vinyl acetate content, 45 weight 96) emulsion (resin solid content: 20 weight %) were mixed at a weight ratio of 10:90. The mixture was coated with a roll coater type coach ink device to obtain a foam laminate. The thickness of the resin layer of the foam laminate obtained was 0.5 mm. Next, the surface resistivity of the foamed laminate obtained was the same as in Example], the half-life of the charge, the bleed-out, and the Plotskink shear force were the same as in Example 2, and the printability and vapor deposition properties were further evaluated. It was measured using the following method. The results are shown in Table 3. (Printability) Printing ink for polypropylene (PPST), cellophane (CC3T: both manufactured by Toyo Ink Manufacturing) #5
0 bar coater, dried in a hot air dryer at 80°C, and then cut out a 20cm long piece of Chiban ■ 1 width 24m + m:) and pasted 15cm of it onto cellophane adhesive tape on the printed area. I rubbed it a few times to make sure the cellophane adhesive tape stuck. The remaining tape portion was quickly peeled off by hand, and the printability was examined by observing how the peeled ink portion remained on the foam. Printability was evaluated using a 5-grade evaluation standard based on the amount of ink remaining on the foam on the peeling surface of the tape. (Evaluation basis $) Less than 50% Index 150% or more ~ 7
Less than 5% Index 275% or more - less than 90%
Index 390% or more - less than 100% Index 4
100% Index 5 Note that a passing score is 4 or higher. (Vapor deposition properties) Made by Chiban ■ on cellophane adhesive tape on the deposition surface, width 24m
After pasting m), 180°C at a speed of 50m+/min.
Judgment was made using the following evaluation criteria based on the adhesion area of the vapor-deposited metal after peeling. (Evaluation criteria) Vapor deposition area after peeling Index 100% Index 590% or more ~ 1
Less than 00% Index 470% or more - less than 90%
Index 350% or more - less than 70% Index 2
Less than 50% Index: 1 Note that a passing score is 4 or higher. Example 8 13 parts of azodicarbonamide was added as a foaming agent to 100 parts of low density polyethylene (density 0.921 g/coi, melt index + 3.2 g/10 min) and mixed to form a foamable resin composition. I got it. Next, the obtained foamable resin composition was introduced into an extruder heated to 120 to 130°C, and melted and kneaded so as not to decompose the foaming agent to obtain a foaming sheet having a thickness of 1.5 mra. Further, this material was irradiated with an electron beam of 3.2 Mrad to cause crosslinking, and then foamed using a vertical hot air foaming device heated to 250° C. to obtain a foam with a thickness of 3.3 mm and a foaming ratio of 25 times. Next, a mixture of the same polyolefin resin used in Example 3 and the same ethylene-vinyl acetate copolymer emulsion used in Example 7 at a weight ratio of 30.70 was used. A foam laminate was obtained analogously to Example 7. The thickness of the resin layer of the resulting foam laminate was 0.021. Next, the physical properties of the foamed laminate obtained were examined in the same manner as in Example 7. The results are shown in Table 3. Example 9 Linear low density polyethylene (density: 0.925 g/
cIIi, tart index: 5 g/10 min) and low density polyethylene (density: 0.923 g/aA
, melt index: 3g/10 minutes) 30/70
15 parts of azodicarbonamide and 1.5 parts of dicumyl peroxide were added as foaming agents to 100 parts of the mixture at a weight ratio of 100 parts, and mixed to obtain a foamable resin composition. Next, the obtained foamable resin composition is introduced into an extruder heated to 120 to 130°C, and care is taken to prevent the blowing agent from decomposing and dicumyl peroxide to decompose and crosslinking to not proceed significantly during kneading. After melting and kneading as described above, the mixture was adjusted to a degree of crosslinking suitable for foaming, and then formed into a foaming sheet. This thing is equipped with a floating device, 2
Foamed in a horizontal hot air foaming device heated to 50°C to a thickness of 4
A foam with a foaming ratio of 35 times was obtained. The same polyolefin resin used in Example 4 and an ethylene-acrylic acid copolymer (acrylic acid content = 25% by weight) emulsion (resin solid content = 30% by weight) were mixed at a weight ratio of 20:80. The material was coach inked in the same manner as in Example 8 to obtain a foam laminate. The thickness of the resin layer of the obtained foam laminate was 0.02 mm. Next, the physical properties of the obtained foam laminate were investigated in the same manner as in Example 7. The results are shown in Table 3. Example 10 Ethylene-propylene copolymer (ethylene content, 8% by weight, melt index: 23g/IO) 100
15 parts of azodicarbonamide and 2 parts of divinylbenzene as foaming agents were added and mixed to obtain a foamable resin composition. Next, the obtained foamable resin composition was introduced into an extruder heated to 170 to 180°C, and melted and kneaded so as not to decompose the foaming agent to obtain a foaming sheet having a thickness of 2.6 mm. Further, this product was crosslinked by irradiation with an electron beam of 2.8 Mrad, and then introduced onto a silicone bath heated to 230°C and foamed to obtain a foam with a thickness of 5 mm and a foaming ratio of 30 times. Formula: 88 mol% of ethylene structural units expressed as ÷CH2-CH2+, formula. Acrylate structure C0 expressed as ÷CH2-CH2+
A polyolefin resin having a weight average molecular weight of 31,300 and consisting of 3 mol% of 0C113 units and 9 mol% of acrylamide structural units represented by the formula: linearly irregularly arranged was pulverized into 32 mesh passes, and Example 9 The same ethylene used in
20% toluene solution of acrylic acid copolymer and 50:5
A foamed laminate was obtained by coating in the same manner as in Example 8 using a mixture with a weight ratio of 0. The thickness of the resin layer of the resulting foam laminate was 0.03 mm. Next, the physical properties of the foamed laminate obtained were examined in the same manner as in Example 7. The results are shown in Table 3. Example 11 100 parts of the same ethylene-propylene copolymer used in Example 10 was mixed with 4 parts of azodicarbonamide and 2 parts of divinylbenzene as blowing agents to obtain a foamable resin composition. Using the obtained foamable resin composition, a foam was obtained in the same manner as in Example 7. The resulting foam had a foaming ratio of 8 times and a thickness of 3. A mixture of the same polyolefin resin used in Example 5 and the same ethylene-acrylic acid copolymer emulsion used in Example 7 at a weight ratio of 30+70 was used, and the same procedure as in Example 8 was carried out. A foam laminate was obtained by coating. The thickness of the resin layer of the resulting foam laminate was 0.08 degrees. Next, the physical properties of the foamed laminate obtained were examined in the same manner as in Example 7. The results are shown in Table 3. [Left below] Comparative Example 6 Polypropylene with melt index of 2.8 g/
A foam was obtained in the same manner as in Example 7 using a 10-minute foam. The resulting foam has an expansion ratio of 6 times and a thickness of 2.5 m.
It was m. Ethylene-vinyl acetate copolymer (containing vinyl acetate:
45% by weight) and chlorinated polyethylene (degree of chlorination = 34
15% by weight) of a mixture of 70/30
A foam laminate was obtained by coach inking in the same manner as in Example 8 using a % toluene solution. The thickness of the resin layer of the obtained foam laminate is 0.02w+
There was m. Next, the physical properties of the foamed laminate obtained were determined in the same manner as in Example 7. The results are shown in Table 4. Comparative Example 7 The same low-density polyethylene as that used in Example 8 was used, the foaming ratio was 20 times, and the thickness was 41.
! 111 foams were obtained. Next, a foamed laminate was obtained in the same manner as in Example 8 using the same ethylene-vinyl acetate emulsion as in Example 8. The thickness of the resin layer of the obtained foam laminate is 0.05ml
Met. Next, the physical properties of the foamed laminate obtained were examined in the same manner as in Example 7. The results are shown in Table 4. Comparative Example 8 Using the same mixture of linear low-density polyethylene and low-density polyethylene as used in Example 9, foams with an expansion ratio of 30 times and a thickness of 5 were made in the same manner as in Example 9. I got it. Next, using an emulsion (resin solid content: 30% by weight) in which an ethylene-acrylic acid copolymer (acrylic acid content: 25% by weight) was neutralized with caustic soda, the foam obtained above was applied in the same manner as in Example 1. A foam laminate was obtained by coating. The thickness of the resin layer of the foam laminate obtained was 0.01 m1. Next, the physical properties of the foamed laminate obtained were examined in the same manner as in Example 7. The results are shown in Table 4. Comparative Example 9 Using the same ethylene-propylene copolymer as that used in Example 9, the expansion ratio was 35 times,
A foam with a thickness of 31I11 was obtained. Next, using a 18% toluene solution of ethylene-acrylic acid copolymer (acrylic acid content: 25% by weight), the obtained foam was coated in the same manner as in Example 9 to form a foam laminate. I got it. The thickness of the resin layer of the resulting foam laminate was 0.009 mm. Next, the physical properties of the foamed laminate obtained were examined in the same manner as in Example 7. The results are shown in Table 4. Comparative Example 10 Using the same ethylene-propylene copolymer as used in Example 11, the foaming ratio was 10 times and the thickness was 311111.
The foam was obtained. Ethylene-acrylic acid copolymer (acrylic acid-containing Ji: 2
5% by weight) and dodecylhensensulfonic acid sorta.
Using an emulsion (resin solid content: 20% by weight) mixed at a weight ratio of 0:10, the obtained foam was coated in the same manner as in Example 11 to obtain a foam laminate. The thickness of the resin layer of the foam laminate obtained was 003+ nm. Next, the physical properties of the foamed laminate obtained were examined in the same manner as in Example 7. The results are shown in Table 4. [As is clear from the results shown in Table 3 below, the foamed laminate of the present invention has an excellent surface resistivity of 1×1013 Ω or less, a charge half-life of 180 seconds or less, and contains antistatic components. It can be seen that there is no bleed-out, no blocking occurs, and the printability and vapor deposition properties are also extremely excellent. On the other hand, as is clear from the results shown in Table 4, conventional foam laminates have poor adhesion and vapor deposition properties, even if they have satisfactory antistatic properties due to the surfactant added as an antistatic agent. I understand that there is something. From the above, the polyolefin resin foam laminate of the present invention has excellent antistatic properties, and there is no bleed-out of the antistatic agent and no blocking occurs.
For example, it is suitable for use in fields where it is necessary to prevent problems caused by static electricity, and in packaging and packaging materials that require printing and vapor deposition. [Effects of the invention] The polyolefin resin foam laminate of the present invention exhibits excellent antistatic properties with no bleed-out, so it does not attract dust and does not cause shock to the human body due to static electricity discharge. Therefore, it is a foam laminate with excellent adhesion, printability, vapor deposition and handling properties.

Claims (1)

[Claims] 1 Formula: ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ 65 to 99 mol% of ethylene structural units, General formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R ^1 indicates an alkyl group having 1 to 4 carbon atoms) 0 to 15 mol% of acrylate structural units and general formula: ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (In the formula, R^2 indicates an alkyl group having 2 carbon atoms) ~8 alkylene group, R^3
and R^4 are each an alkyl group having 1 to 4 carbon atoms, R
^5 is an alkyl group having 1 to 12 carbon atoms, an arylalkyl group having 1 to 12 carbon atoms, or an alicyclic alkyl group having 1 to 12 carbon atoms, X is a halogen atom, CH_3OSO_3 or C
A polyolefin resin layer containing a polyolefin resin having a weight average molecular weight of 1,000 to 50,000 arranged irregularly in a linear manner and consisting of 1 to 35 mol% of acrylamide structural units represented by _2H_5OSO_3) is provided. Polyolefin resin foam laminate.