TW201012649A - Polyolefin resin-laminated foam - Google Patents

Abstract

This objective of the invention relates to a polyolefin resin-laminated foam capable of being applied to a packaging material that is suitable for precision electronic equipment like electronic appliances, precision machines, circuit base plates, silicon semi-conductors, and glass substrates for display and capable of providing excellent washing performance to contaminant transferred on the precision electronic equipment while using water or a cloth containing water to wipe and rinse the contaminant on the surface of the precision electronic equipment. The characteristics of the polyolefin resin-laminated foam are that: the polyolefin resin-laminated foam formed by the polyolefin resin layer is laminated on at least one surface of the polyolefin resin foam layer; more than one hydrophilic compound is selected from a poly epoxide and a surfactant which the HLB (hydrophilic lipophilic balance) value is above 8, and for 100 percent by weight of polyolefin resin that forms the resin layer in the polyolefin resin layer, the aforementioned hydrophilic compound is not actually added into the aforementioned polyolefin resin-laminated foam while simultaneously adding under a ratio between 0.5 and 20 weight percentage.

Description

[Technical Field] The present invention relates to a polyolefin-based resin laminated foam, which is specifically capable of being used as an electronic product, a precision machine, a circuit substrate, a germanium semiconductor, a glass substrate for a display, and the like. A polyolefin-based resin laminated foam suitable for cushioning materials and packaging materials for machines. © [Prior Art] Conventional polyolefin-based resin extruded foamed sheets are widely used for packaging materials such as household electrical appliances, glassware, and ceramics because they are flexible and cushioned, and can prevent damage or scratches of the packaged articles. In addition, in recent years, with the development of thin-type televisions and the increase in demand, the foamed sheet of polyolefin-based resin has been used as a packaging material for a glass substrate for display, and new technical issues have been created. Various techniques for the extruded foamed sheet have been made. Improvement. In the case of the above-mentioned foamed sheet, for example, the glass substrate for a glass substrate is disclosed in the above-mentioned Japanese Patent Application Laid-Open Publication No. 2007-262409. A very high level of surface cleanliness is required. However, when the above-mentioned extruded foamed sheet is used as the packaging material of the glass substrate, the leakage material caused by the additive or the raw material used for the extrusion of the foamed sheet may leak on the surface of the extruded foamed sheet, which is leaked to the surface of the foamed sheet. The leaking material is transferred to an electronic precision machine, which has the concern of contaminating the surface of the electronic precision machine. In addition, since it is easy to accumulate static electricity and is charged by the extruded foam sheet, it has the property of attracting dust in the air to the surface of the foamed sheet, and when the foamed sheet is pressed to package an electronic precision machine, the attracted dust is printed by the assembly board. Precision machines have the suspicion of contaminating the surface of electronic precision machines. On the other hand, in the case of an electronic precision machine, in order to improve the surface cleansing property, the surface cleaning step after taking out a packaging material such as a foamed sheet is indispensable, and in the surface cleaning step, the surface of the electronic precision machine is made of water. When it is washed or wiped with a sheet containing water, it can remove contaminants such as dust, worms, and leaking substances. Therefore, even if the contaminant adheres to the electronic precision machine, it can be removed only by washing with water or the like, and the surface of the electronic precision machine can be cleaned. However, depending on the type of the contaminant and the cleaning method, the removal of the contaminant is sometimes insufficient, which is a cause of defective products of the electronic precision machine. The problem of surface contamination of an electronic precision machine or the like caused by such a foamed sheet is not sufficiently solved. The present invention provides a packaging material which can be used as a packaging material for a precision electronic device such as an electronic product, a precision machine, a circuit substrate, a germanium semiconductor, or a glass substrate for a display, and even if it is transferred to a precision electronic device, it is washed with water or contains water. It is intended to provide a polyolefin-based resin laminated foam which is excellent in cleaning performance when the contaminant on the surface of a precision electronic device is cleaned by wiping the cloth. 201012649 [Means for Solving the Problems] The present inventors have found that when a hydrophilic compound having a hydrophilic-lipophilic balance (HLB値) of 8 to 20 is contained in a polyolefin-based resin foam, in the washing step which is indispensable in the subsequent step, In the case of a precision electronic device, the water-repellent property is improved, and even if the transfer-precision precision machine has been used to clean the difficult-to-clean contaminants in the past, it can be easily removed by washing with water or the like. At the same time, since the hydrophilic compound and the polyolefin resin have poor compatibility, the foam can be produced, but the foaming property is lowered to make the production difficult, and a new problem arises, and the hydrophilic compound generally has a low molecular weight. A new problem in which the mechanical strength of the foam itself is also reduced is also reduced. In particular, when the foam is used as a paper for a glass substrate for a liquid crystal display, since sufficient toughness is required, when a hydrophilic compound is added to the foam, it is necessary to increase the toughness strength, and it is necessary to increase the appearance density and the like. . On the other hand, in order to improve the detergency of the hydrophilic compound, the hydrophilic compound does not need to be contained in the entire foam, and is in contact with the vicinity of the surface of the foam of the packaged product, and contains an amount capable of exhibiting detergency. A hydrophilic compound is sufficient. Therefore, the inventors of the present invention have set a non-foamed resin layer on the surface of the foam, and attempted to add a hydrophilic compound to the resin layer to complete the present invention. The present invention provides the polyolefin-based resin laminated foam shown below. [1] A polyolefin-based resin laminated foam which is obtained by laminating a polyolefin-based resin layer on at least one surface of a polyolefin-based resin foam layer, One or more of the 201012649 hydrophilic compounds selected from the group consisting of a polyepoxide and a surfactant having a hydrophilic-lipophilic balance (HLB値) of 8 or more, and a polyolefin constituting the resin layer in the polyolefin-based resin layer The 1 part by weight of the resin is added in a ratio of 0.5 to 20 parts by weight, and the hydrophilic compound is not added to the polyolefin-based resin foam layer. [2] The polyolefin-based resin laminated foam according to the above 1, wherein the polyepoxide is polyethylene oxide. [3] The polyolefin-based resin laminated foam according to the above 1 or 2, wherein the polyepoxide is in a liquid state at a temperature of 20 °C. [4] The polyolefin-based resin laminated foam according to any one of the above-mentioned, wherein the hydrophilic compound has a number average molecular weight of 100 or less. [5] The polyolefin-based resin laminated foam according to any one of the above-mentioned first aspect, wherein a polyolefin-based resin and a compatibilizing agent of the hydrophilic compound are added to the polyolefin-based resin layer. [6] The polyolefin-based resin laminated foam according to any one of the above-mentioned 1 to 5, wherein the amount of the hydrophilic compound added to the polyolefin-based resin laminated foam is The foam is 2 parts by weight or less in terms of 100 parts by weight. The polyolefin-based resin laminated foam according to any one of the above-mentioned, wherein the polyolefin-based resin foam layer is an extruded foam having an apparent density of 10 to 200 g/L. It is 0.2~2mm. [8] The polyolefin-based resin laminated foam according to the above-mentioned item 7, wherein the polyolefin resin layer is laminated by a pressure-bonding of the polyolefin-based resin foam layer to -8 to 201012649. The polyolefin-based resin laminated foam according to any one of the above-mentioned first aspect, wherein the polymer-based antistatic agent is 100 parts by weight of the polyolefin-based resin. When the ratio is 2 to 30 parts by weight, the surface resistivity of the resin layer is 1 x 10 8 to 1 χ 1014 (Ω). [10] The polyolefin-based resin laminated foam according to the above-mentioned item 9, wherein the polymer type antistatic agent is an antistatic agent containing a block copolymer of a polyether and a polyolefin as a main component. [Effect of the Invention] The polyolefin-based resin laminated foam of the present invention is one or more kinds of hydrophilic compounds selected from the group consisting of an epoxide and a surfactant having a hydrophilic-lipophilic balance (HLB値) of 8 or more, in a specific amount. By laminating the foam, even if contaminants such as dust, worms, and leaking substances are transferred to the surface of an electronic precision machine such as an electronic product, a precision machine, a circuit substrate, a semiconductor, or a glass substrate for display, The contaminants are simultaneously transferred to the surface of the electronic precision machine, and the electronic precision machine can be easily removed by simultaneously washing the water or washing it with a sheet containing water to easily remove the contaminants and the hydrophilic compound. In particular, when transferring to the surface of an electronic precision machine, even if a contaminant that is difficult to clean such as metal ions or oligomers such as sodium ions is transferred from the laminated foam to the surface of the electronic precision machine, only the hydrophilic compound can be present. It is easily removed by the surface of the electronic precision machine by simple cleaning. Further, in the polyolefin-based resin laminated foam of the present invention, the hydrophilic compound is added to the resin layer, but is not substantially added to the foam layer. Therefore, the aqueous compound of the parent--9-201012649 does not inhibit the foaming property. Therefore, the obtained laminated foam has excellent mechanical strength. [Best Mode of Carrying Out the Invention] The polyolefin-based resin laminated foam of the present invention will be described in detail below. The polyolefin-based resin laminated foam of the present invention (hereinafter may be simply referred to as a laminated foam) is a polyolefin-based resin foam layer (hereinafter may be simply referred to as a foam layer), and the foaming A laminate of a polyolefin resin layer (hereinafter also referred to simply as a resin layer) laminated on at least one surface of the bulk layer. In the foam layer constituting the laminated foam of the present invention, a polyolefin resin is used as a foam of a base resin. The polyolefin resin is a resin having an olefin component of 50 mol% or more. Examples of the polyolefin resin include a polyethylene resin and a polypropylene resin. The polyolefin resin is excellent in surface hardness and excellent in flexibility, and is excellent in surface protection of the packaged body. In particular, the polyethylene resin has excellent flexibility and is excellent in surface protection of the packaged body. Therefore, it is better. The polyethylene-based resin is, for example, a resin having an ethylene component of 50 mol% or more, and examples thereof include high-density polyethylene, low-density polyethylene, linear low-density polyethylene, ethylene-vinyl acetate copolymer, and ethylene. - propylene copolymer, ethylene-propylene-butene-1 copolymer, ethylene-butene-1 copolymer, ethylene-hexene-1 copolymer, ethylene-4-methylpentene-1 copolymer, ethylene-octane Further, the ene-1 copolymer may be a mixture of two or more thereof, such as -10-201012649. Among these polyethylene resins, a polyethylene resin having a density of 93 5 g/L or less is preferably used as a main component in consideration of foamability. Specifically, a low-density polyethylene or a linear low-density polyethylene is preferred, and a low-density polyethylene having excellent foaming properties is preferred. When the polyethylene resin having a density of 93 5 g/L or less is used as the "main component", the content of the polyethylene resin is 50% of the total weight of the foam layer.

0% by weight or more. In addition, the lower limit of the density of the polyethylene-based resin is approximately 890 g/L. Further, the polypropylene-based resin may be a copolymer of a propylene single polymer or a component other than a olefin copolymerizable with propylene. Examples of other olefins copolymerizable with propylene include ethylene, or 1-butene, isobutylene, 1-pentene, 3-methyl-1-butene, 1-hexene, and 3,4-di. An α-olefin having 4 to 10 carbon atoms such as methyl-1-butene, 1-heptene or 3-methyl-1-hexene. Further, the copolymer may be a random copolymer or a block copolymer, and not only φ may be a binary copolymer or a ternary copolymer. Further, it is preferred that the other component copolymerizable with propylene in the copolymer is contained in an amount of 25% by weight or less, particularly preferably 15% by weight or less. Further, the lower limit of the content of the other component which can be copolymerized is about 0.3% by weight in consideration of the reason for selecting the copolymer. Further, these polypropylene resins may be used in combination of two or more kinds. Further, the polyolefin resin has a melting point of 100 to 170 ° C. The melting point of the polyolefin resin can be measured in accordance with the method of JIS K7 121-1987. Namely, pretreatment was carried out by the condition adjustment of the test piece (2-11 - 201012649) in JIS K7121-1987 (however, the cooling rate was 10 ° C / min), and the temperature was raised by l 〇 C / min. 'Get the melting peak. The temperature of the resulting peak of the melting peak is used as the melting point. When there are two or more melting peaks, the peak temperature of the main melting peak (the peak with the largest area) is used as the melting point. And the sum of the peaks of the peak areas of the peak area of 8 〇 % or more with respect to the peak area having the largest area is the sum ’ of the peak apex temperature of the peak and the peak apex of the maximum area as a melting point. In the polyolefin-based resin of the present invention, a styrene resin such as polystyrene, an elastomer such as ethylene propylene rubber, or polybutene may be added to the extent that the purpose and effect of the foam layer in the present invention are not inhibited. Butylene resin, etc. The amount of addition at this time is preferably 40% by weight or less, more preferably 25% by weight or less, and particularly preferably 10% by weight or less. Further, the polyolefin resin may contain, for example, a bubble regulator, a nucleating agent, an antioxidant, a heat stabilizer, a weathering agent, an ultraviolet absorber, a flame retardant, and an antibacterial agent in a range that does not inhibit the effects of the object of the present invention. Additives such as functional additives such as shrinkage preventive agents and inorganic chelating agents. The thickness of the laminated foam of the present invention is not particularly limited, but when the foam layer is an extruded foam, the thickness is as large as 0·2 to 1 mm, and in the case of a sheet, it is 0.2 to 0.2. 20mm. Further, when the thickness of the sheet-like extruded foam is too small, the cushioning property and the surface protective property of the electronic precision machine may be insufficient. When the thickness is too thick, the amount of load on the electronic precision machine may be lost. From this point of view, the thickness of the flaky extruded foam is 0.2 to 2.0 mm, preferably 0.2 to 1.5 mm, preferably 0.3 to 1 mm, and particularly preferably 0.3 to 0.7 mm 〇-12- 201012649 The laminated foam of the invention preferably has an apparent density of 10 to 200 g/L. The foamed body layer preferably has a density of the laminated foam when the foam is extruded, and is preferably from 10 to 200 g/L, more preferably from 15 to 180 g/L, particularly preferably from 20 to 100 g/L. When the appearance density of the laminated foam is too high, there is a fear that surface protection is lowered. On the other hand, when the apparent density is too low, there is a fear that the mechanical strength such as conformality or compressive strength of the laminated foam is lowered. In particular, when the laminated foam is in the form of a sheet, the strength of the toughness associated with sagging is lowered. Further, from the viewpoint of the surface protective property, the laminated foam preferably has an appearance density of 150 g/L or less, preferably 120 g/L or less, more preferably 100 g/L or less. Further, the foaming sheet having high toughness is minimized when supported by a single-fixed beam. From this viewpoint, the apparent density is preferably 20 g/L or more, preferably 30 g/L or more, more preferably 40 g/ L or more. Further, when the foam layer is a sheet-like extruded foam, the laminated foam is preferably weighed at 10 to 80 g/m2, more preferably 12 to 60 g/m2, still more preferably 15 to 50 g/m2. Good for 20~40g/m2. The flatness is only 1 Og/m2 or more φ, which ensures the toughness strength, and only 80g/m2 or less does not cause excessive cost increase. The thickness of the entire laminated foam in the present invention is an arithmetic mean 厚度 of the thickness (mm) measured at intervals of 1 cm in the width direction over the entire width of the laminated foam. The apparent density of the laminated foam in the present invention is obtained by dividing the weight (g) of the test piece cut out from the laminated foam by the volume (cm3) obtained from the outer shape of the test piece. Unit conversion (g/L). Further, when the foam layer is a pressure-extracted foam, the average cell diameter is from the viewpoints of mechanical properties such as stretching of the foam layer of -13 to 201012649, appearance, surface smoothness, and surface protection of the packaged article. The average bubble diameter in the extrusion direction and the width direction is preferably 0.2 to 0.8 mm, preferably 0.3 to 0.7 mm, more preferably 0.4 to 0.6 mm. The average bubble diameter of the foam layer is such that the foam layer is The width direction and the extrusion direction perpendicular to the width direction are cut, and the measurement is performed according to the cross section that appears. Specifically, the photograph is enlarged in the width direction of the foam layer, and the length of the foam layer is divided into two equal parts and a length of 30 mm (in consideration of the enlargement ratio of the enlarged photograph, the length line of the enlargement ratio of 30 mm by the enlargement ratio) The center line of the line finds the number of bubbles (η) that intersect the line. The average diameter of the bubble diameter in the width direction is determined by the calculation formula of 30/(η-1) according to the length of the line of 30 mm and the number of bubbles (η) sought. The other wide-direction cross-sections of the foam layer were similarly operated, and the wide-direction bubble diameters at five places were repeatedly calculated to obtain the average enthalpy, and these arithmetic mean enthalpies were used as the average bubble diameter in the width direction of the foam layer. Further, the measurement was carried out in the same manner as in the measurement method of the average cell diameter in the width direction, in addition to the measurement of the cross-sectional area in the extrusion direction of the foam layer, and the average cell diameter in the extrusion direction of the foam layer. In the polyolefin-based resin laminated foam of the present invention, a polyolefin-based resin layer is laminated on at least one surface of the foam layer. The polyolefin-based resin constituting the resin layer in the present invention, the other resin or the additive added thereto, and the like are the same as those described above for the foam layer. However, the structure of the foam layer and the resin layer are not necessarily the same, and the two may be laminated only, and the polyolefin resin may be of a different composition. The amount of the resin layer is preferably 55 g/m2 or more per side, preferably 201012649 0.7 g/m2 or more, more preferably lg/m2 or more. The amount of the resin layer to be weighed is within the above range, and the desired detergency can be sufficiently exhibited. From the viewpoint of detergency, the upper limit of the weighing amount is not limited, but from the viewpoint of cushioning property or lightness, the upper limit is preferably 1 g/m 2 or less, preferably 60 g/m 2 , more preferably It is 50 g/m2 or less. In particular, when the resin layer is formed by co-extrusion, since the thickness of the resin layer can be made thin, the amount of the resin layer is preferably 0.5 to 10 g/m2, preferably 0.7 to 5 g/m2, more preferably 1 to 1. 3g/m2. φ Further, the thickness of the resin layer is preferably uniform, but it may be within the range of the object and effect of the present invention, and the thickness may be uneven. In the present invention, the weighing amount of the resin layer can be determined by any of the following two methods. In the first method of weighing measurement, the vertical cross section of the laminated foam is appropriately enlarged by a microscope or the like, and the thickness of the resin layer is measured at 10 points in the width direction at equal intervals, and the arithmetic mean enthalpy obtained is used as the average of the resin layer. The thickness is multiplied by the density of the base resin constituting the resin layer, and the weight of the resin layer [g/m2] is obtained in units of conversion. However, this method is limited only to the case where the interface between the tree φ lipid layer and the foam layer is clear. In the second method of measuring the amount of the laminated foam, when the laminated foam is produced by co-extrusion, when the laminated foam is produced, the amount of discharge from the resin layer X [kg/hour] and The width W [m] of the obtained laminated foam and the length L [m/hr] of the laminated foam per unit time can be determined by the following formula (1) [g/m2]. Further, when the resin layer is laminated on both sides of the foam layer, the amount of each resin layer can be determined by the amount of discharge of each resin layer. Weighing 4/1112] = [1000 again / (1 > '^)]..* (1) In the laminated foam of the present invention, since the resin layer contains a specific hydrophilic -15-201012649 compound, the resin is used. When the side of the layer is packaged on the packaged body, even when the contaminants such as dust, worms, and leaking substances are transferred from the resin layer to the surface of an electronic precision machine such as an electronic product, a precision machine, a circuit board, a semiconductor, or a glass substrate for a display. By transferring the hydrophilic compound and the contaminant to the surface of the electronic precision machine at the same time, the electronic precision machine can be cleaned by water alone or wiped with a sheet containing water to clean the contaminant and the hydrophilic substance. The compound is easily removed at the same time. In particular, it is difficult to wash metal ions or oligomers such as sodium ions, and it is necessary to carry out the cleaning to remove the contaminants which can be removed, even if the resin layer is transferred to the surface of the electronic precision machine, only the hydrophilic compound is present. These contaminants can be easily removed from the surface of an electronic precision machine by simple washing. The hydrophilic compound to be added to the resin layer is one or more compounds selected from the group consisting of polyepoxides and surfactants having 8 or more HLB値. Further, a polymer type antistatic agent to be described later may be added to the resin layer of the present invention, and the polymer type antistatic agent may contain a polyepoxide or the like. However, the polyepoxide or the like contained in the polymer type antistatic agent is contained in a small amount as a copolymer component or the like in a polymer type antistatic agent, and is used for improving the antistatic property. The polyepoxide in the polymer type antistatic agent is equal to the amount of the polyepoxide added to the resin layer as a hydrophilic compound in the present invention, and does not affect the specificity of the present invention. When the amount of the hydrophilic compound added is in the range of the amount, the effect of improving the detergency of the packaged article which can achieve the object and effect of the present invention cannot be expected. Examples of the epoxide having a carbon number of 2 to 6 as the epoxide constituting the polyalkylene oxide include, for example, ethylene oxide-16-201012649 (ethylene glycol) and propylene oxide (propylene glycol). ), 1,2-butylene oxide, 1,4·butylene oxide, 2,3-butylene oxide, 1,3-butylene oxide, butylene oxide (butanediol), epoxy Pentane (pentanediol), hexylene oxide (hexanediol), and the like. Two or more kinds of epoxides can be used as the polyepoxide. Among the polyepoxides, polyethylene oxide (polyethylene glycol) is preferred from the viewpoint of easy availability and easy handling. The HLB(R) in the present invention can be blended with the type of the hydrophilic compound, and φ is obtained by the Atlas method or the Griffin's method known in the art as described below.

Atlas method (in the case where the hydrophilic compound type is an ester-based surfactant) HLB = 20 ( 1 -S/A ) S: saponification A: acid value of the fatty acid constituting the hydrophilic compound Griffin's method (type of hydrophilic compound) When the state is other than the ester-based surfactant, HLB = 2〇x The molecular weight of the hydrophilic group portion/the total amount of the hydrophilic compound is φ. When the HLB is less than 8, the detergency may be insufficient or may be attached to the display. Contaminants on the surface of electronic precision machines such as glass substrates cannot be easily removed. From this point of view, it is preferable that HLB is preferably 10 or more, and 15 or more is preferable. Further, the upper limit of the HLB of the surfactant is less than 20 〇 In the present specification, the HLB of the polyepoxide is determined by the Griffin's method. Specifically, for example, when the polyepoxide is formed of a copolymer of polyethylene oxide and a polyepoxide other than the polyethylene oxide, the polyethylene oxide is regarded as a hydrophilic group-17-201012649 portion, and the polymerization is further The epoxide, which is determined to be a hydrophilic group or a hydrophobic group in consideration of its hydrophilicity to hydrophilicity, is obtained by Griffin's method. Further, in the case of polyethylene oxide, all of them are hydrophilic groups, so the upper limit of the HLB of the polyepoxide is 20. As the surfactant having an HLB of 8 or more, only HLB値 is 8 or more, and any type of surfactant can be used. Among them, a polyepoxide-based surfactant which is also a nonionic surfactant is preferable. The polyepoxide-based surfactant is preferably a polyepoxide, and an epoxide-added nonionic surfactant is preferred. Specific examples of the polyepoxide-based surfactant include an oxyalkylene alkyl ether (for example, octanol). Ethylene oxide adduct, lauryl alcohol ethylene oxide adduct, stearyl alcohol ethylene oxide adduct, oleyl alcohol ethylene oxide adduct, lauryl alcohol oxide propylene oxide block Adducts, etc.); polyoxyalkylene higher fatty acid esters (such as ethylene glycol adducts of stearic acid, ethylene oxide adducts of lauric acid, etc.): polyoxyalkylene polyols higher fatty acid esters (eg poly Ethylene glycol lauric acid diester, polyethylene glycol oleic acid diester, polyethylene glycol stearic acid diester, etc.; polyoxyalkylene alkylphenyl ether (such as nonylphenol ethylene oxide plus Compound, nonylphenol ethylene oxide propylene oxide block adduct, octylphenol ethylene oxide adduct, bisphenol A ethylene oxide adduct, dinonyl phenol ethylene oxide a product, a styrenated phenol ethylene oxide adduct, etc.; a polyoxyalkylene alkylamine ether and (for example, a laurylamine ethylene oxide adduct, a stearylamine ring) Ethane adduct, etc.): polyoxyalkylene alkyl alkanoate (for example, ethylene oxide adduct of hydroxyethyl laurate decylamine, ethylene oxide adduct of hydroxypropyl oleate decylamine) , an ethylene oxide adduct of dihydroxyethyl lauric acid decylamine, etc.). -18-201012649 Among the above hydrophilic compounds, one or more kinds of polyepoxide-based surfactants having a polyepoxide and an HLB値 of 8 or more are preferable, and a polyepoxide is preferable. The polyepoxide in the present invention is preferably a liquid at a temperature of 20 ° C. A polyepoxide which is solid at 20 ° C can exhibit excellent detergency when an oligomer or a metal ion can be removed by water, and 2 (TC is a liquid polyepoxide or the like by a resin layer. It is easy to leak, and it is more easily dissolved in water. Therefore, it is excellent in the detergency of impurities such as oligomers or metal ions which are difficult to wash by water, etc. From this point of view, 1 〇 °c is liquid. It is preferred that it is liquid at o °c, preferably liquid at -10 °c, and liquid at -20 °c. For the same reason, poly ring The number average molecular weight of the oxide or the above surfactant is preferably 1,000 or less, preferably 600 or less. Further, the lower limit is greater than 150. Further, the number average molecular weight of the polyepoxide can be calculated from the acid base price. Further, when the number average molecular weight of polyepoxide is difficult to be calculated from the hydroxyl value, it is determined by high temperature gel permeation chromatography. The amount of the hydrophilic compound added to the resin layer is The 100% by weight of the polyolefin resin of the resin layer is a ratio of 0.5 to 20 parts by weight. When the amount of the compound added is less than 0.5%, the detergency may be insufficient, or contaminants adhering to the surface of an electronic precision machine such as a glass substrate for a display may not be easily removed. On the other hand, the added amount exceeds 20% by weight. In the case of the detergent, there is no problem in terms of detergency, and the amount of addition not only affects the detergency, but when the amount of addition is too large, when the resin layer is formed, the aqueous compound is separated from the resin layer, and the resin cannot be formed. From the viewpoint of the layer, it is preferable that the amount of the hydrophilic compound added to the resin layer is preferably from 1 to 15 parts by weight based on the weight of the polyolefin resin constituting the resin layer. It is preferably from 1.5 to 12 parts by weight, more preferably from 2 to 10 parts by weight, particularly preferably from 3 to 7 parts by weight. In the resin layer of the present invention, it is preferred to fuse the polyolefin-based resin with a hydrophilic compound, and In order to suppress the separation of the two, it is preferable to add a compatibilizing agent. Examples of the compatibilizing agent include a copolymer of a polyolefin and a hydrophilic polymer, and specific examples thereof include a copolymer of a polyolefin and a polyether, and the like. Rear In the present invention, substantially no hydrophilic compound is added to the polyolefin resin foam layer. Substantially no addition means that no hydrophilic compound is added to the foamed layer, or even if it is added. The foaming property is not impaired, and the amount of mechanical strength is not reduced as compared with the case of no addition. The amount of addition is 0.4 parts by weight or less based on 100 parts by weight of the polyolefin resin constituting the foam layer. However, it contains 0), preferably 0.3 part by weight or less (but contains ruthenium), more preferably 0.1 part by weight or less (but contains 0), and no addition is particularly preferable. Moreover, as a possibility of adding a hydrophilic compound to the foamed layer The use of the recycled raw material may result in a violation of the intention, even if it is not intentionally added. The polyolefin-based resin laminated foam (laminated foam) of the present invention has the above-mentioned 'having a polyolefin-based resin. A multilayer structure of a foam layer (foam layer) and a polyolefin resin layer (resin layer) laminated on the surface -20-201012649. Further, in the resin layer, since a specific amount of the hydrophilic compound is added, excellent detergency can be exhibited. On the other hand, since the foam layer is substantially free of a hydrophilic compound, the foam layer is not hindered by the foaming property due to the hydrophilic compound, and can be a laminated foam having excellent mechanical strength. Further, since the hydrophilic compound added to the resin layer does not inhibit the foaming property, the concentration of the hydrophilic compound can be increased, and the detergency is higher than that of the single-layer foam. Further, even if the amount of addition of the hydrophilic compound in the entire laminated foam is high, the amount of the hydrophilic compound added in the single layer structure of the foam layer is small, so the laminated foam is small. Under the same conditions and the same thickness, it has the same mechanical strength as the single-layer foam. The laminated foam of the present invention contains a form in which both the resin layer is laminated on one side of the foam layer and the resin layer is laminated on both sides. When the resin layer is laminated on both sides, the hydrophilic compound may be added to only one side or may be added to both sides. When the laminated foam of the present invention is used as a paper between glass substrates φ, it is preferred that the resin layer to which the hydrophilic compound is added is laminated on both sides of the foam layer. The amount of the hydrophilic compound added to the entire laminated foam is not more than 2 parts by weight based on 100 parts by weight of the laminated foam, from the viewpoint of not lowering the mechanical strength of the laminated foam. Preferably, it is preferably 1.5 parts by weight or less, more preferably 1 part by weight or less. Further, in the laminated foam of the present invention, since the hydrophilic compound is not substantially added to the foam layer, the closed cell ratio of the laminated foam can be easily maintained as compared with the case where the hydrophilic compound is added to the foam layer. Higher. As a laminate, the closed cell ratio of the foam is preferably 40% or more, and more preferably 50% or more, from the viewpoint of the surface protective properties and the mechanical strength of the packaged article. The independent bubble ratio of the above laminated foam is determined according to ASTM-D2 8 5 6-7 0, step C, using an air comparison type hydrometer 930 type of Toshiba Beckman Co., Ltd. (will be cut by laminated foam) A sample piece of 2 5 mm X 2 5 mm X 2 0 mm was placed in a sample cup for measurement. Further, if the laminated foam was too thin to cut a sample piece of the above size, a 25 mm x 25 mm X laminate of a plurality of pieces was cut out. The sample of the thickness of the foam was superimposed to have a true volume Vx of the laminated foam (sample piece) of the sample for measurement of 25 mm x 25 mm x about 20 mm, and the independent bubble ratio S was calculated by the following formula (1). (%). S(%) = (Vx-W/p)x 100/(Va-W/p) (1)

Vx: The true volume (cm3) of the sample slice measured by the above method corresponds to the sum of the volume of the resin constituting the sample slice and the total volume of the bubble of the individual bubble portion in the sample slice.

Va: The apparent volume (cm3) of the sample slice calculated from the outer dimensions of the sample slice used for the measurement. W: The total weight (g) of the sample slice used was determined. P: density of the resin composition obtained by defoaming the laminated foam (g/cm3) The surface resistivity of the resin layer can be set by adding a polymer type antistatic agent to the resin layer of the present invention. Lxio8~1χ1014(Ω). -22- 201012649 When the surface resistivity is too large, the antistatic property will be insufficient, or an electrostatic charge will accumulate on the surface of the resin layer, and dust will easily adhere. In order to prevent dust from adhering, the surface resistivity is preferably 5 χ 1013 Ω or less, and more preferably 1 χ 1013 Ω or less. On the other hand, when the surface resistivity is too small, there is no problem in the antistatic property, but the antistatic property required on the packaging material is excessive and there is a concern that the cost is too high. The surface resistivity in the present specification is measured in accordance with JIS Κ 6271 (2001) after the state of the following test piece is adjusted. In other words, the test piece cut out from the laminated foam of the object to be measured (length 100 mm×100 mm×thickness: thickness of the test piece) was placed in an environment of temperature 3 (TC, relative humidity of 30% for 36 hours, and then test piece was taken. The state is adjusted, and the voltage is applied in accordance with JIS K6271 (2001) with a voltage of 500 kV, and the surface resistivity after 1 minute is obtained. To make the surface resistivity of the resin layer ΙχΙΟ8~1χ1〇14Ω, The olefin-based resin layer is preferably a polymer type antistatic agent having a ratio of 2 φ to 30 parts by weight based on 100 parts by weight of the polyolefin resin. When the amount is too small, there is a fear that the antistatic property may not be exhibited. On the one hand, when the amount of addition is too large, there is no problem in terms of antistatic property, but the antistatic property reaches the limit, so the cost performance is poor. From this point of view, the antistatic agent is added in an amount of 4 to 30. The parts by weight are preferably 6 to 25 parts by weight. The number average molecular weight of the antistatic agent is preferably 2,000 or more, preferably 2,000 to 100,000, more preferably 5,000 to 60,000, particularly preferably 8,000 to 40.千. Therefore, the antistatic agent is a polymer type antistatic agent which can be distinguished from the antistatic agent formed by the surfactant -23-201012649. Moreover, the number average of the antistatic agent of the polymer type When the number average molecular weight of the polymer type antistatic agent is within the above range, the antistatic agent is placed in the package, and the surface of the package is not contaminated. The number average molecular weight can be obtained by high temperature gel permeation chromatography. For example, when the polymer type antistatic agent is a hydrophilic resin containing a polyether ester decylamine or a polyether as a main component, o-dichlorobenzene is used as a solvent to prepare a sample. The concentration is 3 mg/ml, and the polystyrene is used as a reference material at a column temperature of 135 ° C. The type of the solvent and the column temperature can be matched with the type of the polymer antistatic agent. The polymer type antistatic agent used in the present invention is a hydrophilic resin having a volume resistivity of 1 〇 5 to 1 〇 η·cm and a copolymer with a polyolefin. Can use polyether two a polyether such as a polyether diamine or a denature thereof, and a polyether ester decylamine having a segment of a polyether diol as a polyether segment forming component, and a polyether segment forming component can be used as a poly As the polyether segment forming component, a polyether ester having a segment of a polyether diol can be used as a polyether segment forming component, and a polyether diamine can be used as a polyether segment forming component. As the polyether oxime in the segment, a polyether such as a polyether urethane having a segment of a polyether diol or a polyether diamine may be used as a polyether sulfonate-containing polyether having a hydrophilic resin and having a nonionic ion in the molecule. a cationic polymer having 2 to 80, preferably 3 to 60 cationic groups, a dicarboxylic acid having a sulfonyl group, and a diol or a polyether as a constituent unit, and a molecule An anionic polymer having 2 to 80, preferably 3 to -24 to 201012649, 60 sulfonyl groups. In addition, in the polymer type antistatic agent, it is desired to improve the compatibility with the polyalkylene-based resin, and to provide an antistatic effect, and to suppress the decrease in physical properties by adding an antistatic agent, the same type as the polyolefin resin or The polyolefin-based resin having a high compatibility is preferably a block copolymerization, and examples thereof include a block having a polyolefin and a block of the hydrophilic resin having a volume resistivity of 105 to 1 ΐ Ω·cm. The number average molecular φ (?η) of the structure which is repeatedly cross-linked is 2000 to 60,000 block copolymer. Among them, block copolymers of polyether and polyolefin (block copolymer) are more preferable than the above-mentioned compatibility. Further, the block of the polyolefin and the block of the hydrophilic resin have a repeated interaction via at least one bond selected from the group consisting of an ester bond, a guanamine bond, an ether bond, a urethane bond, and an imine bond. Combined structure. Further, a block of a polyolefin of the above-mentioned block polymer which is preferably used as a polymer type antistatic agent, a polyolefin having a carboxyl group at both terminals of the polymer, and a polyolefin having a carbonyl group at one end of the polymer are preferred. . More specifically, the polymer type antistatic agent as described above is a composition described in JP-A No. 3-103466 and JP-A No. 2001-2780985. The composition described in JP-A-3-103466 is a block copolymer containing (I) a thermoplastic resin, (poly)polyethylene oxide or a polyethylene oxide block component of 50% by weight or more, and (III) The metal salt of the polyethylene oxide block component in the above (II) is a solid solution, and the composition described in JP-A No. 2001-278985 has a polyalkylene hydrocarbon ( The block of a) and the block of the hydrophilic resin (b) having a volume resistivity of ΙχΙΟ5~ΙχΙΟ^Ω. -25- 201012649, the number average molecular weight (Μη) of the structure which is repeatedly cross-linked is 2000~ Block copolymer of 60000. The block of the above (a) and the block of (b) have a bond interposed by at least one selected from the group consisting of an ester bond, a guanamine bond, an ether bond, a urethane bond, and an imine bond. Combined structure. As such a polymer type antistatic agent, for example, "SD100" manufactured by Mitsui, DU PONT POLYCHEMICALS Co., Ltd., and "PELESTAT300" manufactured by Sanyo Chemical Industries Co., Ltd., are commercially available. Each of the above-mentioned polymer type antistatic agents may be used singly or in combination of plural kinds. Further, the melting point of the polymer type antistatic agent is preferably 70 to 270 ° C, more preferably 80 to 230 ° C, and particularly preferably 80 to 200 ° C, but from the viewpoint of the performance of the antistatic function It is better. The melting point of the polymeric antistatic agent can be measured by the following method in accordance with JIS K7121 (1987). That is, pretreatment was carried out by the condition adjustment (2) of the test piece in JIS K7121 (1987) (however, the cooling rate was 10 ° C /min), and the melting peak was obtained by 1 (TC/min heating). The peak temperature of the obtained melting peak is used as the melting point. When two or more melting peaks appear, the temperature of the peak of the melting peak of the largest area is used as the melting point. To achieve the desired surface resistivity, the foam layer is not required. When the polymer-based antistatic agent is added, when the recovered material of the laminated foam is used as a raw material for the foam layer, when the polymer antistatic agent is added, the foam layer contains a polymer antistatic agent. Even in this case, the content of the polymer type antistatic agent is 15 parts by weight of the polyolefin resin constituting the foam layer, and 15 The mechanical strength of the laminated foam is preferably 5 parts by weight or less, preferably 3 parts by weight based on 100 parts by weight of the polyolefin resin constituting the foam layer. Below the weight Next, a method for producing the polyolefin-based resin laminated foam of the present invention will be described. φ The foam layer constituting the laminated foam of the present invention may be produced only by extrusion foaming, and may be produced. The foam particles are produced by an in-mold forming method in which heating and melting are performed in a metal mold. Further, as a method of laminating the resin layer to the foam layer, a hydrophilic compound may be added to the surface of the previously produced foam layer. The film is produced by lamination by thermal lamination or lamination by extrusion lamination, or by co-extrusion method in which a foam layer and a resin layer are extruded by a mold. When the in-mold forming method is used, a film containing a hydrophilic compound prepared in advance can be melted into a foamed particle molded body in a metal mold. When the foamed layer is a pressed foam, it is co-extruded. In the method, a resin layer to which an antistatic agent is added is laminated on a foam layer to carry out extrusion foaming, whereby the thickness of the resin layer can be reduced, and a laminate having a high adhesion between the resin layer and the foam layer can be obtained. Bubble body Preferably, the method for producing a sheet-like laminated foam by a co-extrusion method has a method in which a flat die for co-extrusion is used in a sheet form, and a method of co-extrusion foaming and lamination is used, and a method of co-extrusion is used. Ring-molded mold and cylindrical cooling device, method of co-extrusion foaming of cylindrical laminated foam, and slitting of cylindrical laminated foam to make -27-201012649 a lamellar laminated foam In the above, the method of using a ring-shaped mold for co-extrusion suppresses the generation of a corrugated mold called corrugate, or it is easy to produce a laminated foam having a wide width of 1000 mm or more, which is preferable. For the case of co-extrusion using the above-mentioned co-extrusion annular mold, the details are as follows. As shown in Fig. 1, first, the polyolefin resin (A1) and the hydrophilic compound (B) are necessary. The polymer type antistatic agent (C) to be added is supplied to the resin layer forming extruder 11, and after being heated and melted and kneaded, a volatile plasticizer (D) is added as necessary, and after melt-kneading, it becomes a polyolefin. A resin melt (E1) for forming a resin layer. At the same time, an additive (G) such as a polyolefin-based resin (A2) and a bubble adjusting agent to be added as needed is supplied to the foam layer forming extruder 12, and is heated and melted, kneaded, and then pressed into a physical foaming agent (F). After the kneading, the resin-formed resin melt (E2) is formed into a polyolefin-based resin foam layer. Further, when the hydrophilic compound (B) is a liquid hydrophilic compound (B 1 ), it can be added by indentation together with the volatile plasticizer (D), and the hydrophilic compound (B) is a solid hydrophilic compound. In the case of (B2), the base material using the polyolefin resin may be added simultaneously with the polyolefin resin (A1), or the solid hydrophilic compound (B2) may be heated to be liquid, and then added by press-fitting. In the case of the co-extrusion method, only the resin melt (E1) for forming the resin layer in the annular mold and the resin melt (E2) for forming the foam layer can be used. Lamination is performed outside each other outside the mold exit. Further, the above-mentioned annular mold, extruder, cylindrical cooling device, and apparatus for cutting a cylindrical laminated foam of -28-201012649 can be used for a person who has been used in the field of extrusion foaming in the past. When a volatile plasticizer is added to the resin-based resin layer (E1) for forming a polyolefin resin layer, the volatile plasticizer (D) has a function of lowering the melt viscosity of the resin melt (E1) and is used for polymerization. After the olefin-based resin layer (J) is formed, it is more likely to volatilize than the polyolefin-based resin layer and is not present in the resin layer. When the volatile plasticizer (D) is added to the φ resin melt (E1) and the laminated foam is pressed together, the extrusion temperature of the resin layer-forming resin melt (E1) is close to the foam layer. When the extrusion temperature of the resin (E2) for forming is formed, the improvement of the melt extension of the resin layer (J) in the molten state can be remarkably improved. Therefore, the foam layer is hardly broken by the foam structure of the hot foam layer at the time of foaming, and the elongation of the resin layer (J) follows the elongation at the time of foaming of the polyolefin resin foam layer (I). Therefore, cracking can be prevented by the insufficient extension of the resin layer (J). As the volatile plasticizer (D), one type or two or more types selected from the group consisting of aliphatic hydrocarbons having 2 to 7 carbon atoms, aliphatic alcohols having 1 to 4 carbon atoms, and aliphatic ethers having 2 to 8 carbon atoms are used. It is better. When the volatile agent is generally used as a plasticizer, a lubricant or the like remains on the resin layer (J), which may contaminate the surface of the package. The resin of the resin layer (J) can be plasticized efficiently with respect to the volatile plasticizer (D), and it is preferable that the volatile plasticizer itself is hard to remain in the obtained resin layer (J). Examples of the aliphatic hydrocarbon having 2 to 7 carbon atoms include ethane, propane, n-butane, isobutane, n-pentane, isopentane, neopentane, cyclopentane, n-hexane, and isohexane. , cyclohexane, n-heptane, and the like. -29- 201012649 Examples of the aliphatic alcohol having 1 to 4 carbon atoms include methanol, ethanol, propanol, butanol, isopropyl alcohol, isobutyl alcohol, n-butyl alcohol, and sec-butyl alcohol. , tert-butyl alcohol. Examples of the aliphatic ether having 2 to 8 carbon atoms include dimethyl acid, diethyl acid, propyl acid, isopropyl acid, methyl ethyl ether, methyl propyl ether, and methyl group. Propyl ether, methyl butyl ether, methyl isobutyl ether, methyl amyl ether, methyl isoamyl ether, ethyl propyl ether, ethyl isopropyl ether, ethyl butyl ether, B Isobutyl ether, ethyl amyl ether, ethyl isoamyl ether, vinyl ether, allyl ether, methyl vinyl ether, methyl allyl ether, ethyl vinyl ether, ethyl allyl ether . Since the boiling point of the volatile plasticizer (D) can be easily volatilized by the resin layer (J), it is preferably 120 ° C or lower, preferably 80 ° C or lower. When the boiling point of the volatile plasticizer (D) is only in this range, after the co-extrusion, only the obtained laminated foam (H) is placed, and the heat after co-extrusion is further used to further the room temperature. The lower gas is transmitted, and the volatile plasticizer (D) is naturally volatilized by the resin layer (J) of the laminated foam, and is naturally removed. The lower limit of the boiling point is -50T槪-50T:. The amount of the volatile plasticizer (D) to be added is 100 parts by weight of the kneaded product of the polyolefin-based resin (A1) and the hydrophilic compound (B) and, if necessary, the polymer-based antistatic agent (C). In other words, it is preferably 5 parts by weight to 50 parts by weight. The addition amount of the volatile plasticizer (D) is only 5 parts by weight or more, and heat generation due to shearing during kneading of the polyolefin resin constituting the resin layer (J) can be suppressed, and the laminated resin layer (J) The resin -30-201012649 of the resin layer-forming resin melt (E2) formed by the foam layer (I) is suppressed in temperature (temperature reduction effect). Therefore, when the resin layer-forming resin melt (E2) is foamed, it is possible to prevent the bubbles from being damaged or the like. In addition, the volatile plasticizer (D) can improve the elongation (stretching property improvement effect) of the resin layer-forming resin melt (E2) for foam layer formation of the resin layer-forming resin melt (E1) during foaming, and also has The effect of uniformly forming the thickness of the resin layer (J) is thin. From this viewpoint, the amount of the volatile plasticizer (D) to be added is preferably 7 parts by weight or more, and more preferably 10 parts by weight or more. On the other hand, the addition amount of the volatile plasticizer (D) is only 50 parts by weight or less based on 100 parts by weight of the polyolefin-based resin (A1), and does not cause deterioration in physical properties of the resin layer (J) itself, and is volatile. The plasticizer (D) is impregnated into the resin layer-forming resin melt (E1), and can be sufficiently kneaded. Therefore, the volatile plasticizer is not ejected from the lip, and the resin layer (J) is not opened, or The surface has irregularities and the surface smoothness is lowered. From this viewpoint, the amount of the volatile plasticizer (D) to be added is preferably 40 parts by weight or less, more preferably 30 parts by weight or less, still more preferably 25 parts by weight or less. When the amount of the volatile plasticizer (D) to be added is in the above range, the temperature-reducing effect and the stretchability-improving effect of the resin layer-forming resin melt at the time of co-extrusion can be ensured. Further, in the resin layer-forming resin melt (E1), various additives may be added in a range not inhibiting the object of the present invention. Examples of the various additives include an antioxidant, a heat stabilizer, a weather resistance agent, an ultraviolet absorber, a flame retardant, a chelating agent, and an antibacterial agent. The amount of the polyolefin resin (A1) forming the melt (E1) is preferably -31 to 201012649 by weight or less, more preferably 5 parts by weight or less, and preferably 3 parts by weight or less. The following is especially good. The lower limit is 重量·〇1 parts by weight. Examples of the physical foaming agent (F) include aliphatic hydrocarbons such as propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, and isohexane, and lipids such as cyclopentane and cyclohexane. Organic physical foaming agents such as chlorinated hydrocarbons such as cyclic hydrocarbons, methyl chloride and chlorinated ethane, and fluorinated hydrocarbons such as 1,1,1,2-tetrafluoroethane and 1,1-difluoroethane; An inorganic foaming agent such as oxygen, nitrogen, carbon dioxide or air, or a decomposable foaming agent such as azobiscarbonamide. The above physical foaming agent may be used in combination of two or more kinds. Among them, an organic foaming agent is preferred from the viewpoint of compatibility with a polyethylene resin and foaming property, and n-butane, isobutane, or a mixture thereof as a main component is also preferable. It is better. As the main additive (G), a bubble regulator is generally added. As the bubble adjusting agent, any of an organic type or an inorganic type can be used. Examples of the inorganic bubble adjusting agent include boric acid metal salts such as zinc borate, magnesium borate, and borax, sodium chloride, aluminum hydroxide, talc, zeolite, ceria, calcium carbonate, and sodium bicarbonate. Further, examples of the organic bubble adjusting agent include phosphoric acid-2,2-extended methylbis(4,6-tert-butylphenyl)sodium, sodium benzoate, calcium benzoate, aluminum benzoate, and stearic acid. Sodium and so on. Further, a combination of citric acid, sodium bicarbonate, citric acid, an alkali metal salt, sodium bicarbonate or the like may be used as the bubble regulator. These bubble modifiers can be used in mixture of 2 or more types. The amount of the physical foaming agent (F) to be added can be adjusted in accordance with the type of the foaming agent and the apparent density of the object. Further, the amount of the bubble adjusting agent added can be adjusted in accordance with the purpose of the bubble diameter. For example, as a foaming agent, a butane mixture of 30% by weight of isobutane and 70% by weight of n-butane is used, and when the laminated foam having the density of 201012649 is obtained, the amount of the butane mixture added is for the polyolefin system. The resin (A2) is 100 parts by weight, preferably 3 to 3 parts by weight, preferably 4 to 2 parts by weight, more preferably 6 to 18 parts by weight. In addition, the amount of the air-conditioner to be added is 0.1 to 1 part by weight, preferably 0.03 to 8 parts by weight, per 100 parts by weight of the polyolefin-based resin (A2). In the resin melt (E2) for forming a polyolefin resin foam layer, other resins such as benzene φ ethylene resin or elastomer, or thermal stability may be added as long as the object and effect of the present invention are not inhibited. Additive for the agent. When the laminated foam is produced by co-extrusion, the resin layer-forming resin melt (E1) is formed using an extruder, and the foam layer-forming resin melt is formed using the extruder 12 (E2). The resin melt (E2) is adjusted to a foamable temperature in the extruder 12, and the resin melt (E1) is adjusted to a temperature which can be co-pressed in the extruder 11, and then the resin layer is formed. The resin melt (E1) and the resin layer-forming resin melt (E2) are introduced into the co-extrusion annular mold 13 to laminate the two, and are simultaneously pressed in the atmosphere to cause foaming. The resin layer-forming resin melt (E2) is foamed, and is formed into a cylindrical laminated foam of the foam layer laminated resin layer, and the inner surface of the cylindrical laminated foam is cooled along the cylindrical cooling device. - At the same time, the slit is opened to obtain a laminated foam (H). However, the resin layer-forming resin melt (E1) and the foam layer-forming resin melt (E2) are laminated so as to be laminated only inside the ring mold 13, and may be in the vicinity of the outlet, or Lamination is carried out outside the mold exit. [Embodiment] - 33 - 201012649 [Examples] Hereinafter, the present invention will be described in more detail based on examples. However, the invention is not limited by the examples. As the bubble adjusting agent, a bubble conditioner masterbatch prepared by adding 20% of talc (trade name "High filler #12" manufactured by Matsumura Co., Ltd.) to 80% by weight of the polyethylene resin was used. As a polyolefin resin for forming a foam layer and a resin layer, a low density polyethylene "NUC8321" (density: 922 g/L, MFR: 2.4 g/10 min) manufactured by Unicar Co., Ltd., Japan was used. As a polymer type antistatic agent, a polyether-polypropylene block copolymer manufactured by Sanyo Chemical Industries Co., Ltd. was used as a main component of "Pelestat 3 00" (melting point 136 ° C, number average molecular weight 14000, density 990 g / L). As the physical foaming agent, a mixed butane of 70% by weight of n-butane and 30% by weight of isobutane was used. The hydrophilic compounds used are shown in Table 1. -34- 201012649 [Table 1] Compound name HLB Properties (20〇C) Number average molecular weight impurity 1 Polyethylene glycol 20 mk 300 Chemically mixed 2 Polyethylene glycol 20 Solid 2000 Compound 3 Polyethylene oxide polyepoxy Polyoxyethylene polyoxypropylene block copolymer 16 solid 8750 compound 4 polyethylene glycol 20 occupation 600 compound 5 stearic acid polyethylene glycol ester 11.9 solid 670 chemical 6 glyceryl stearate 12 solid 1000 compound 7 Glycerol monostearate 4.3 "Solid 350 compound 8 Tetraglyceryl stearate 5.6 Solid 570 Compound 9 Propylene glycol monolaurate 4.2 Juru 240 and Compound 3 is 20% by mass of polypropylene oxide as the constituent component The polypropylene oxide exhibits hydrophilicity at a low molecular weight, but exhibits hydrophobicity as the molecular weight increases. In the compound 3, the number average molecular weight of the polyacrylic acid compound component is larger than 1750, so the polypropylene oxide component Hydrophobicity was observed. HLB 値 was calculated by considering the polypropylene oxide-based portion as a hydrophobic group portion. Examples 1 to 9 and Comparative Examples 1 to 5 were formed as a polyolefin-based resin foam layer. The extruder (12) is a two-seat extruder made of a first extruder having a diameter of 115 mm and a second extruder having a diameter of 150 mm, and is used as an extruder for forming a polyolefin resin layer (11). A third extruder having a diameter of 65 mm and an L/D = 50 is used, and each of the outlets of the second extruder and the third extruder is connected by a ring-shaped mold for co-extrusion, and each molten resin is ring-shaped. The mold can be laminated in the mold. -35- 201012649 The low-density polyethylene "NUC832 1" which is a polyolefin resin and the hydrophilic compound of the type and amount shown in Table 2 are supplied to the raw material input port of the third extruder. The mixture was heated and kneaded, and the mixed butane in an amount shown in Table 2 was injected as a volatile plasticizer, and kneaded further to adjust the temperature of the extruded resin shown in Table 2 as a resin melt for resin layer formation. The resin layer-forming resin melt was introduced into a ring-shaped mold for co-extrusion at a discharge amount as shown in Table 2. Further, in Examples 1, 3, and 9 and Comparative Example 5, "PELESTAT300" was added as a high molecular type antistatic agent in a ratio shown in Table 2. However, the liquid hydrophilic compound was added in the same manner as the physical foaming agent, and a solid hydrophilic compound was prepared using a low-density polyethylene "NUC83 2 1" as a masterbatch of a matrix resin concentration of 10% by weight. Add to as quantified as. At the same time, the low-density polyethylene "NUC 8 32 1 " which is a polyolefin resin and the bubble conditioner masterbatch of the amount shown in Table 3 are supplied to the raw material input port of the first extruder of the two-seat extruder. The mixture was heated and kneaded as a molten resin mixture adjusted to about 200 °C. Next, a physical foaming agent in an amount as shown in Table 3 was injected into the molten resin mixture, and secondarily supplied to a second extruder connected to the downstream side of the first extruder, and the temperature was adjusted as shown in Table 3. The temperature of the resin to be extruded is used as a resin melt for foam layer formation, and the resin melt for foam layer formation is introduced into the annular mold for coextrusion in the discharge amount shown in Table 3. The outer side and the inner side of the resin melt for forming a foam layer which is introduced into the annular mold for coextrusion and introduced in a ring shape are laminated and introduced into the common extrusion ring-36-201012649. In the resin layer-forming resin melt, the laminate of the melt is molded into the atmosphere by molding, and a cylindrical laminate foam composed of three layers of a resin layer/foam layer/resin layer is formed. The extruded cylindrical laminated foam was cut along the cooled cylindrical cooling device (mandrel) at a drawing speed shown in Table 3 to obtain a laminated foam. Reference Example 1 g As an extruder for forming a polyolefin resin foam layer, use

A two-seat extruder of a first extruder having a diameter of 115 mm and a second extruder having a diameter of 150 mm is connected to the annular mold at the outlet of the second extruder. The low-density polyethylene "NUC 832 1" which is a polyolefin resin and the bubble conditioner masterbatch of the amount shown in Table 2 are supplied to the raw material input port of the first extruder of the two-seat extruder, and are heated. The mixture was adjusted to about 200 ° C as a molten resin mixture. Then, the "Compound 1" described in Table 1 was pressed as a hydrophilic compound in a ratio of 3.1 parts by weight to 100 parts by weight of the polyolefin resin φ, and the physical amount shown in Table 2 was pressed. The foaming agent is supplied to the second extruder connected to the downstream side of the first extruder, and the temperature is adjusted to the temperature of the resin extruded as shown in Table 2, and the foam layer is formed as a resin layer for foam layer formation. The resin melt for formation was introduced into the annular mold in the amount of discharge shown in Table 3. The melt is pressed out of the atmosphere by a mold to form a cylindrical foam formed only of the foam layer. The extruded cylindrical foam was cut while being pulled along the cooling mandrel to obtain a foamed body. -37- 201012649

[S resin layer extraction amount (kg/hour) S surface side κη vd κη vd in V) ν〇\ό •«Η 'd νη 'Ο ^0 m 'Ο 1 Μ面侧\ό \Τ) 'Ο Vd ir> F—Η V) V£) »r> m νο •-Η iTi v〇ιρ^ vi iTi SO Laminated surface 1 on both sides 1 膣 2 sides 1 2 sides 1 1 2 sides! 1 2 sides 1 2 sides 1 2 sides 1 1 Mm 1 two sides 1 two sides 1 1 two sides | 1 two sides and two sides of the extrusion temperature (°C) VO ν〇ν〇*-Η Ό ^-Η VO \〇«-Η ν〇Τ"*Η V〇^-Η ν〇 Η \〇SO Volatile plasticizer (parts by weight) <N <N <Ν CN (Μ (N cs (N CN n) <s CS high liver type antistatic agent (parts by weight) 1 I 1 1 1 1 1 I 1 1 τ—Η Hydrophilic compound addition method 1 Direct press 1 | Direct press in | 1 Direct press in I Masterbatch masterbatch 1 Direct press in 1 Masterbatch masterbatch masterbatch Masterbatch|Direct press in | | Direct press in I 1 Direct press in 1 Add amount (parts by weight) — 〇CN ο 卜 — 卜 — — Ο CN 卜 寸 · C^; — 〇〇m 〇〇 (S m • ΤΝΤΝ itmll m 丨 compound lj 1 compound 1| 丨 compound ι| 丨 compound 2| 丨 compound 3j 丨 compound 4" 丨 compound 5| 丨 compound ό | 丨 compound 6| 丨 compound 7j 丨 compound 8 ! 丨 compound 9| 丨 compound 11 丨 compound lj poly olefin resin _ £ i i i ο ο 〇ο 〇Ο 〇〇〇〇 Category 1 NUC8321 1 NUC8321 NUC8321 NUC8321 NUC8321 NUC8321 NUC8321 NUC8321 NUC8321 NUC8321 NUC8321 NUC8321 NUC8321 NUC8321 丨 Example 1 I | Example 2 I j Example 3 1 | Example 4 ] 1 Example 5 I 1 Example 6 1 | Example 7 I Example 8 | Example 9 I Comparative Example 1 丨 Comparative Example 2 | Comparative Example 3 I | Comparative Example 4 I Comparative Example 5 Reference Example 1 1}総令莛脃8二|} aiming ^§^^鲫菊啪啪啪濉1}闽2^_93±1* .1_葙?^__001^_味«奖跋§^制_长«"^ __"旮谳* -38- 201012649 [ε® Pulling speed (m/min) (N cK (N & iT) Os cs a; iTi <N iTi CN o; V) Ό (N (N a: m N ( Y/Ί On m as ma\ ON U^i Os ο 2 Pressure Temperature L (°〇) CN 1 H CN CN «—1 04 oj rj OJ <Ν inchΜ Μ尔_ 刍w r4 (N r"H <N 卜o fH r4 卜o CN CN ψ^< oi (N (N CN c〇^Η bubble modifier masterbatch (parts by weight) κη <nr*^ in Ui in ν£> ^Η Polyolefin resin blending amount (parts by weight) 〇ooooooooo 〇ooooo 〇o O 2 o 〇oo Ο ο Ο Ο Ο ι~Η Type NUC8321 NUC8321 NUC8321 NUC8321 NUC8321 NUC8321 NUC8321 | NUC8321 1 NUC8321 NUC8321 NUC8321 NUC8321 NUC8321 NUC8321 1 NUC8321 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Implementation Example 7 I Example 8] Example 9 Comparative Example 1 1 Comparative Example 2 I 1 Comparative Example 3 1 1 Comparative Example 4] Comparative Example 5 丨 Reference Example 1. Stupid _3- f - φδοο- i^l^siiiil" -- _oIM}siNI_0QIlgl-N1 义i "甶__"旮漱* -39- 201012649 The laminated results obtained from the examples, comparative examples and reference examples The evaluation of the thickness, appearance density, weighing, average cell diameter, surface resistivity, and detergency of the foam body is shown in Table 4.

-40- 201012649 [Inch 漱] Washability ◎ ◎ 〇〇〇 ◎ 〇〇〇XXXX ※ ng #( ◎ Drop amount (mm) 〇CN (Ν κη »-Η cn CN m (N OO CSI surface resistivity ( Ω ) | 8xl010 I 1 2χ1010 1 1 1 1 1 ο X 00 1 1 1 1 1 Average bubble diameter (mm) Width direction L〇.43 丨1 0.42 II 0.45 IL〇:4lJ I 0.40 1 1 0.44 1 | 0.40 1 1 0.44 1 1 0.44 1 0.42 | 0.42 1 1 0.42 1 0.40 | 1 0.42 | Extrusion direction L___ 0.53 0.48 0.40 0.55 | 0.52 | 0.54 0.40 1 0.52 1 0.52 1 L 0.49 0.58 0.51 1 0.41 0.50 Appearance density (g/L m cn VO m Ϊ—H mv〇mm \〇m vo 〇mm class mmv〇 inch o thickness (mm) inch ο inch ο Ο 1 < | 0.35 ! yn ci inch inch o inch inch inch o | 0.35 j inch C5 O Ϊ _ foam layer 1 21.4 1 丨 21.4 1 1 25.6 1 1 21.4 I 1 21.4 | 21-4 | 1 42.8 I 1 21.4 1 Γ 21.4 1 Γ 21.4 Π 1 21.4 I 121.4 1 25.6 | r4 Resin layer I s face side I 00 00 (Ν CN 00 oo OO iH \D rn OO 00 00 OO f-^ 00 <N <N 1 I Μ 侧 side | 00 〇〇(Ν (Ν 00 oo OO v〇cn oo iH 00 00 00 00 <N CN 1 All (Ν CN (N < NU^i CN IT) (N (Ν cs iT) (N in (N 1 embodiment ϊ 1 1 embodiment 2 1 1 embodiment 3 1 1 embodiment 4 1 embodiment 5 embodiment 6 embodiment 7 implementation Example 8 Example 9 1 Comparative Example 丨 1 丨 Comparative Example 2 1 1 Comparative Example 3 1 | Comparative Example 4 1 Comparative Example 5 1 Reference Example 1 1 - <鲫装网妲^& thief 忉松仞^龌 龌 龌 襄 襄 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ <Evaluation method of detergency> The hard-chrome-plated steel sheet was held in a laminated foam on a mirror-shaped stainless steel plate having an average surface rent of 〇·2 μm, and a load of 50 g/cm 2 was applied thereto. It was allowed to stand at 60 ° C for 48 hours. Thereafter, the steel sheet was immersed and washed in pure water. After washing and drying, 'blowing on the surface of the steel sheet and visually observing the condition of the dirt (cloud)' was evaluated according to the following criteria 〇 ◎: completely free of dirt (clouds). 〇: A little bit of dirt (clouds) is present. X: Most of the dirt (clouds) is present. The measurement of the surface resistivity in the laminated foam was carried out as follows. <Measurement of Surface Resistivity> Three test pieces (length 100 mm x width 100 mm x thickness: test piece thickness) cut out from the laminated foam were used as samples. The surface resistivity in the table was measured by placing the test piece at a relative humidity of 30% and a temperature of 30 ° C for 36 hours. After the state of the test piece was adjusted, it was immediately measured at 23 ° C and 50% RH. Surface resistance. At this time, according to the method of JIS K6 271 (2001), the surface resistivity after pressurization to a voltage of 500 V for 1 minute was used, and the surface resistivity of the obtained enthalpy was measured. The measuring device uses "TR8 601" manufactured by Takera Lai Industrial Co., Ltd. Further, the surface resistivity of the laminated foam in which the polymer layer was not added with the polymer type anti-42-201012649 was not measured. <Measurement of the amount of drooping (strength of toughness)> The measurement of the toughness in Table 4 was carried out as follows. A test piece having a width of 100 mm, a length of 200 mm, and a thickness of "laminate foam thickness" was cut into the width direction and test of the laminated foam obtained from the examples, the comparative examples, and the reference examples. The length direction of the sheet is φ, the test piece is placed on the horizontal support table, the mandrel surface side is upward, and the 50 mm part of the length 200 mm is supported by the end of the support table, and the tip end of the test piece leaking is measured. The amount of dangling [mm] was evaluated to evaluate the toughness of the laminated foam. Further, since the amount of sag in the width direction is larger than the direction of extrusion, only the amount of drooping in the width direction is measured. [Brief Description of the Drawings] Fig. 1 is a view showing an example of a method for producing a foamed sheet of the present invention. [Description of main elements and symbols] 11: Presser for forming a resin layer 12: Extruder 13 for forming a foam layer : cyclic molding die A, A2: polyolefin resin B: hydrophilic compound B 1 : liquid hydrophilic compound - 43 - 201012649 B2 : solid hydrophilic compound D : volatile plasticizer E 1 Resin melt E2 for polyolefin resin layer formation: Resin melt for forming polyolefin resin foam layer F: Physical foaming agent G: Additive Η: Laminated foam I: Foam layer J: Resin layer -44-

Claims (1)

201012649 VII. Patent application scope: A polyolefin resin laminated foam which is a polyolefin resin laminated layer formed by laminating a polyolefin resin layer on at least one surface of a polyolefin resin foam layer. The foam is characterized in that one or more hydrophilic compounds selected from the group consisting of a polyepoxide and a hydrophilic-lipophilic balance (HLB値) 8 or more are used to form the resin in the polyolefin-based resin layer. 100 parts by weight of the layer of the polyolefin resin is added at a ratio of 0.5 to 20 parts by weight, and the hydrophilic compound is not substantially added to the polyolefin resin foam layer. 2. The polyolefin-based resin laminated foam according to claim 1, wherein the polyepoxide is polyethylene oxide. 3. The polyolefin-based resin laminated foam according to claim 1 or 2, wherein the polyepoxide is at a temperature of 2 (TC is a liquid. 4. If the patent application is in the first to the first The polyolefin φ-based resin laminated foam of any one of the above-mentioned, wherein the number average molecular weight of the hydrophilic compound is 1 000 or less. 5. The method according to any one of claims 1 to 4 A polyolefin-based resin laminated foamed body in which a polyolefin-based resin and a hydrophilic compound are added to the polyolefin-based resin layer. 6. In the first to fifth aspects of the patent application scope In the polyolefin-based resin laminated foamed body, the amount of the hydrophilic compound added to the polyether-based resin laminated foam is 2 parts by weight based on 100 parts by weight of the laminated foam. The polyolefin-based resin laminated foam according to any one of the above-mentioned items, wherein the polyalkylene-based resin foam layer is an extruded foam, The polyolefin resin laminated foam has an apparent density of 10 to 200 g/L, and is thick. 8. The polyether-based resin laminated foam of the seventh aspect of the invention, wherein the polyolefin-based resin layer is laminated by co-pressing a polyolefin-based resin foam layer The polyolefin-based resin laminated foam according to any one of the first to eighth aspects of the invention, wherein the polyolefin-based resin layer is a polymer-based antistatic agent for a polyolefin system. 100 parts by weight of the resin is added in a ratio of 2 to 30 parts by weight, and the surface resistivity of the resin layer is lxl 〇 8 to 1 x 1014 (Ω). 10. Polyolefin-based resin laminated foam according to claim 9 The polymer type antistatic agent is an antistatic agent containing a block copolymer of a polyether and a polyolefin as a main component.