WO2022210956A1

WO2022210956A1 - Resin foamed body and foamed member

Info

Publication number: WO2022210956A1
Application number: PCT/JP2022/016236
Authority: WO
Inventors: 清明児玉; 亮伊関; 彰吾佐々木
Original assignee: 日東電工株式会社
Priority date: 2021-03-31
Filing date: 2022-03-30
Publication date: 2022-10-06
Also published as: CN116981723A; KR20230164049A; KR20230164050A; JPWO2022210957A1; CN117062861A; WO2022210957A1; JPWO2022210956A1

Abstract

Provided is a resin foamed body that is excellent in light-blocking properties and in punching processability.　This resin foamed body has a foamed structure, has an apparent density of at least 0.03 g/cm³, and satisfies relationship (1): 100Y – 4X > 3, where Y (g/cm³) is the apparent density and X (%) is the light transmittance of the resin foamed body which has been pressed and is in a bulk state. When a load of 1000 g/cm² is applied to the resin foamed body, the thickness recovery rate after the load is maintained for 120 seconds is at least 80%. In one embodiment, the light transmittance X of the resin foamed body which has been pressed and is in a bulk state is not more than 0.02%.

Description

Resin foams and foamed parts

The present invention relates to resin foams and foamed members.

Foam is often used as a cushioning material to protect screens of electronic devices, substrates, and electronic components. 2. Description of the Related Art In recent years, there has been a demand for narrowing the clearance of a portion where a cushioning material is arranged in accordance with the trend toward thinner electronic devices. Furthermore, with the miniaturization and multi-functionalization of electronic equipment, there is a tendency for the electronic components used to be miniaturized, and a smaller cushioning material (foam) is sometimes required. In addition, high light-shielding properties are sometimes required for foams that are applied in the vicinity of members such as cameras where the influence of light should be taken into consideration.

Usually, when obtaining a foam with a desired shape, the raw foam is punched. In punching, a mold is used to apply high pressure to the foam to obtain the desired shape of the foam. In conventional foams, the thickness that is reduced by punching may not fully recover after the punching process, resulting in thickness variations. Such a phenomenon is particularly problematic when applied to a location with a narrow clearance, or when punched into a narrow shape (for example, 1 mm wide) such as a picture frame shape.

Patent Document 1 discloses a resin foam with excellent shock absorption. However, this document neither discloses nor suggests workability (punching workability) at the time of punching. Further, Patent Document 2 discloses a resin foam having a thin layer and excellent shock absorption. However, this document does not disclose recoverability or crushing after punching. Furthermore, a resin foam having both high light-shielding properties and punching workability has not been realized.

Japanese Patent Laid-Open No. 2017-186504 Japanese Patent Application Laid-Open No. 2015-034299 Japanese Patent Application Laid-Open No. 2016-69493

An object of the present invention is to provide a resin foam that is excellent in both light-shielding properties and punchability.

The resin foam of the present invention is a resin foam having a cell structure and an apparent density Y of 0.03 g/cm ³ or more, wherein the light transmittance X (%) in the bulk state after pressing and the apparent density Y (g/cm ³ ) satisfies the relationship of the following formula (1),
100Y-4X>3 (1)
The thickness recovery rate after a load of 1000 g/cm ² is applied to the resin foam and maintained for 120 seconds is 80% or more.
In one embodiment, the light transmittance X in the bulk state after pressing is 2.0% or less.
In one embodiment, the apparent density Y is less than 0.4 g/cm ³ .
In one embodiment, the resin foam has a cell number density of 30 cells/mm ² or more.
In one embodiment, the resin foam has a coefficient of variation of cell diameter of 0.5 or less.
In one embodiment, the resin foam has an average cell diameter of 10 μm to 200 μm.
In one embodiment, the resin foam has a void content of 30% or more.
In one embodiment, the resin foam has a 50% compression load of 20 N/cm ² or less.
In one embodiment, the resin foam contains a polyolefin resin.
In one embodiment, the polyolefin-based resin is a mixture of a polyolefin other than a polyolefin-based elastomer and a polyolefin-based elastomer.
In one embodiment, the resin foam has a hot melt layer on one side or both sides.
According to another aspect of the invention, a foam member is provided. This foam member has a resin foam layer and an adhesive layer disposed on at least one side of the resin foam layer, and the resin foam layer is the resin foam.

According to the present invention, it is possible to provide a resin foam that has excellent punching workability with little change in thickness before and after punching, even after punching. The resin foam of the present invention is also excellent in that it has high light shielding properties.

1 is a schematic cross-sectional view of a foam member according to one embodiment of the invention; FIG.

A. Resin Foam The resin foam of the present invention has a cell structure. Examples of the cell structure include a closed cell structure, an open cell structure, a semi-open and semi-closed cell structure (a cell structure in which a closed cell structure and an open cell structure are mixed), and the like. Preferably, the cell structure of the resin foam is a semi-open and semi-closed cell structure. Typically, the resin foam of the present invention is obtained by foaming a resin composition. The resin composition is a composition containing at least a resin constituting a resin foam. The resin foam has an apparent density Y of 0.03 g/cm ³ or more.

In the resin foam, the light transmittance X (%) in the bulk state after pressing and the apparent density Y (g/cm ³ ) satisfy the relationship of the following formula (1). Preferably, the relationship between the light transmittance X (%) in the bulk state after pressing, the apparent density Y (g/cm ³ ), and the following formula (1)′ is satisfied. By satisfying such a relationship between the light transmittance X (%) and the apparent density Y (g/cm ³ ) in the bulk state after pressing, a resin foam having excellent light blocking properties can be obtained. In one embodiment, "100Y-4X" is less than 8 (preferably 6, more preferably 4).
100Y-4X>3 (1)
100Y-4X>3.5 (1)'

In this specification, the "bulk state after pressing" means a state in which all air bubbles in the resin foam are removed by crushing the resin foam. In one embodiment, hot pressing creates a "pressed bulk state." For example, it is pressed at a temperature higher than the melting point of the resin forming the resin foam.

Also, in this specification, the "light transmittance X in the bulk state after pressing" means the transmittance of light with a wavelength of 550 nm in the thickness direction of the bulk state test piece after pressing with a thickness of 0.03 mm. The bulk state test piece after pressing with a thickness of 0.03 mm is a resin foam that has been adjusted in advance as necessary so that the thickness of the test piece in the bulk state is 0.03 mm (for example, the thickness is adjusted by slicing, lamination, etc. The molded resin foam) can be obtained by pressing with a predetermined pressing plate to a thickness of 0.03 mm. For example, a test piece can be obtained by sandwiching a 1 mm thick resin foam between aluminum plates (0.5 mm thick), providing a 0.03 mm thick spacer, and applying pressure while applying a temperature equal to or higher than the melting point.

The thickness recovery rate (hereinafter also referred to as instantaneous recovery rate) after a load of 1000 g/cm ² is applied to the resin foam and maintained for 120 seconds is 80% or more. Within such a range, a resin foam having excellent stamping workability can be obtained. More specifically, the resin foam shows favorable behavior such that shape change such as thickness change is small even when it is punched, and even if the thickness is temporarily reduced by punching, it recovers in a short time. , excellent punchability. The instantaneous recovery rate is preferably 80% or higher, more preferably 85% or higher, still more preferably 87% or higher, and particularly preferably 90% or higher. Although the thickness recovery rate is preferably as high as possible, its upper limit is, for example, 99% (preferably 100%). A method for measuring the thickness recovery rate will be described later.

In the present invention, the light transmittance X (%) in the bulk state after pressing and the apparent density Y (g/cm ³ ) satisfy the relationship of the above formula (1), and the instantaneous recovery as described above. When the ratio is within a specific range, it is possible to obtain a resin foam having high light-shielding properties and excellent stamping workability. Thus, it is one of the great results of the present invention that high light-shielding properties can be achieved without impairing punching workability.

The light transmittance X in the bulk state after pressing is preferably 2.0% or less, more preferably 1.0% or less, still more preferably 0.7% or less, still more preferably 0.02. %, particularly preferably 0.01% or less, and most preferably 0.001% or less. Within such a range, a resin foam having excellent light blocking properties can be obtained. The lower limit of the light transmittance X in the bulk state after pressing is, for example, 0.00001%. The light transmittance X in the bulk state after pressing can be adjusted by the composition of the resin composition. In one embodiment, it can be adjusted by the type, amount, etc. of additives and/or fillers (for example, carbon, etc.) in the resin composition.

The apparent density Y of the resin foam is preferably less than 0.4 g/cm ³ , more preferably 0.3 g/cm ³ or less, even more preferably 0.2 g/cm ³ or less, still more preferably It is 0.10 g/cm ³ or less, and particularly preferably 0.05 g/cm ³ or less. The foamability can be judged by the apparent density. One of the characteristics of the resin foam of the present invention is that it has a low apparent density. By having such characteristics, it is possible to provide a resin foam that is excellent in both punching workability and light-shielding properties. Moreover, when the apparent density is within the above range, a resin foam having excellent flexibility and stress dispersion can be obtained. On the other hand, a resin foam having an excessively high apparent density may cause deformation of the application site by pressing. In particular, such a problem becomes conspicuous when applied to a location with a narrow clearance. The lower limit of the apparent density Y of the resin foam is 0.03 g/cm ³ as described above. A method for measuring the apparent density will be described later.

In one embodiment, in the resin foam, the light transmittance X (%) in the bulk state after pressing and the expansion ratio Z (times) satisfy the relationship of the following formula (2). More preferably, the relationship between the light transmittance X (%) in the bulk state after pressing, the expansion ratio Z, and the following formula (2)' is satisfied. More preferably, the relationship between the light transmittance X (%) in the bulk state after pressing, the foaming ratio Z (times), and the following formula (2)'' is satisfied. If the light transmittance X (%) and the foaming ratio Z (times) in the bulk state after pressing satisfy such a relationship, the effect of the present invention becomes remarkable. In one embodiment, "Z+6X" is greater than 0.005 (preferably 0.01). The expansion ratio is calculated by dividing the density in the bulk state after pressing/the apparent density of the resin foam.
Z+6X<30 (2)
Z+6X<20 (2)'
Z+6X<0.05 (2)''

In one embodiment, the resin foam as described above uses a resin having a die swell ratio of 1.4 or less at +20°C (the melting point of the resin that constitutes the resin foam) as the resin that constitutes the resin foam. can be formed by using That is, in one embodiment, the die swell ratio at +20°C of the melting point of the resin forming the resin foam before foaming is 1.4 or less. If a resin having a die swell ratio within the above range is used, shrinkage during formation of the resin foam can be prevented, and a thick resin foam can be formed, and the resin foam can contain cells with a small cell size. The die swell ratio at +20°C of the melting point of the resin forming the resin foam before foaming is preferably 1.2 or less, more preferably 1.1 or less. The lower limit of the die swell ratio of the resin (before foaming) is, for example, 1.05 (preferably 1.02, more preferably 1.01). In addition, the die swell ratio at the melting point +20°C of the resin constituting the resin foam (that is, the resin after foaming) is preferably 1.4 or less, more preferably 1.2 or less, and still more preferably 1. .1 or less. The lower limit of the die swell ratio of the resin (after foaming) is, for example, 1.05 (preferably 1.02, more preferably 1.01). As used herein, the die swell ratio means a value obtained by dividing the diameter of the extruded resin by the diameter of the die when extruding molten resin from a die. The die swell ratio is obtained by extruding a resin melted at a melting point of +20°C using a die having a length of 10 mm and a diameter of 1 mmφ at a shear rate of 20 mm/s, and measuring the diameter of the resulting string-like molding. It is calculated by the formula of diameter (mm) of molding/diameter of die (mm). The melting point of the resin is measured by the peak top temperature of the endothermic peak obtained by differential scanning calorimetry (DSC). Differential scanning calorimetry (DSC) was measured using a differential scanning calorimeter (eg, trade name "Q-2000", TA Instruments) with a sample weight of 3 mg and a heating rate of 10°C/min. Measured under the conditions of When it has two or more peaks, the peak top temperature on the high temperature side is taken as the melting point.

In one embodiment, the resin foam as described above can be formed by using a resin having a shear viscosity of 3000 Pa·s or less at the melting point (the melting point of the resin constituting the resin foam) +20°C. can. That is, in one embodiment, the shear viscosity at +20°C of the melting point of the resin forming the resin foam before foaming is 3000 Pa·s or less. If a resin having a shear viscosity within the above range is used, the gas used for forming the cell structure can be preferably dispersed when forming the resin foam, and as a result, a resin foam with small cell sizes can be obtained. The shear viscosity at +20°C of the melting point of the resin forming the resin foam before foaming is preferably 2500 Pa s or less, more preferably 2100 Pa s or less, still more preferably 2000 Pa s or less, and particularly preferably. is 1900 Pa·s or less. The lower limit of the shear viscosity of the resin (before foaming) is, for example, 500 Pa·s (preferably 700 Pa·s, more preferably 1000 Pa·s). In addition, the shear viscosity at the melting point +20°C of the resin constituting the resin foam (that is, the resin after foaming) is preferably 3000 Pa s or less, more preferably 2500 Pa s or less, and still more preferably 2100 Pa s. s or less, particularly preferably 2000 Pa·s or less, and most preferably 1900 Pa·s or less. The lower limit of the shear viscosity of the resin (after foaming) is, for example, 500 Pa·s (preferably 700 Pa·s, more preferably 1000 Pa·s). In this specification, the shear viscosity can be measured by extruding a resin melted at a melting point of +20° C. using a die having a length of 10 mm and a diameter of 1 mmφ at a shear rate of 20 mm/s.

The thickness of the resin foam is preferably 100 μm to 8000 μm, more preferably 200 μm to 5000 μm, still more preferably 300 μm to 4000 μm, still more preferably 400 μm to 3000 μm, still more preferably 500 μm to 2000 μm. be. Such a range is advantageous in that a fine and uniform cell structure can be formed, and excellent punching workability and impact absorption can be exhibited.

The average cell diameter (average cell diameter) of the resin foam is preferably 10 μm to 200 μm, more preferably 20 μm to 180 μm, still more preferably 40 μm to 150 μm, and particularly preferably 40 μm to 80 μm. Within such a range, it is possible to obtain a resin foam that is more excellent in flexibility and stress dispersibility. In addition, it is possible to obtain a resin foam that is excellent in compression recovery, stamping workability, and resistance to repeated impact. In one embodiment, the resin foam has an average cell diameter (average cell diameter) of 90 μm or less (preferably 80 μm or less). Within such a range, a resin foam having excellent light blocking properties can be obtained. In particular, the effect of improving the light shielding property becomes remarkable in combination with increasing the bubble number density as described later. A method for measuring the average bubble diameter will be described later.

The coefficient of variation of the bubble diameter (cell diameter) of the resin foam is preferably 0.5 or less, more preferably 0.4 or less, still more preferably 0.3 or less, still more preferably 0.3. It is 25 or less, and particularly preferably 0.2 or less. Within such a range, when compressive force is applied by punching or the like, variation in bubble deformation is reduced. With such a resin foam, for example, a processed product (cut product) having excellent thickness accuracy can be obtained when punched. Further, when the coefficient of variation of cell diameter is within the above range, deformation due to impact becomes uniform, local stress load is prevented, and a resin foam having excellent stress dispersibility and particularly excellent impact resistance is obtained. be able to. Although the coefficient of variation is preferably as small as possible, its lower limit is, for example, 0.15 (preferably 0.1, more preferably 0.01). A method for measuring the coefficient of variation of bubble diameter will be described later.

The foam rate (cell rate) of the resin foam is preferably 30% or more, more preferably 50% or more, and still more preferably 80% or more. Within such a range, a resin foam having moderate flexibility can be obtained. Such a resin foam has excellent punching workability, and prevents the occurrence of uncut parts when punched. The upper limit of the void content is, for example, 99% or less. A method for measuring the void content will be described later.

The thickness of the cell wall (cell wall) of the resin foam is preferably 0.1 μm to 10 μm, more preferably 0.3 μm to 8 μm, still more preferably 0.5 μm to 5 μm, and particularly preferably 0.7 μm to 4 μm, most preferably 1 μm to 3 μm. Within such a range, a resin foam having excellent light blocking properties can be obtained. Also, a resin foam having appropriate strength can be obtained. Such a resin foam has excellent punching workability, and is prevented from tearing, dusting, and uncut parts during punching. Moreover, when the cell wall thickness is within the above range, a resin foam having excellent flexibility and stress dispersion can be obtained. In one embodiment, the thickness of the cell wall (cell wall) of the resin foam is 5 μm or less. With such a range, the above effect becomes remarkable. The thickness of the cell wall can be measured by capturing an enlarged image of the cell portion of the resin foam and analyzing the image using the analysis software of the measuring instrument.

When the cell structure of the resin foam is a semi-open and semi-closed cell structure, the proportion of the closed cell structure therein is preferably 40% or less, more preferably 30% or less. In this specification, the ratio of the closed-cell structure of the resin foam is determined, for example, by submerging the object to be measured in water in an environment with a temperature of 23 ° C. and a humidity of 50%, measuring the mass after that, and then measuring the temperature at 80 ° C. It is obtained by measuring the mass again after drying it sufficiently in an oven. In addition, since open cells can hold moisture, the mass of open cells is measured as open cells. The proportion of open cells in the resin foam is preferably higher than 60%, more preferably higher than 70%. Within such a range, a resin foam having excellent light blocking properties can be obtained. The ratio of open cells was also determined by immersing the measurement object in water in an environment of 23 ° C. and 50% humidity, measuring the mass after that, then drying it sufficiently in an oven at 80 ° C., and measuring the mass again. is obtained by measuring

The cell number density of the resin foam is preferably 30 cells/mm ² or more, more preferably 50 cells/mm ² or more, still more preferably 65 cells/mm ² or more, and still more preferably 80 cells/mm 2 or more. /mm ² or more, more preferably 90/mm ² or more, still more preferably 100/mm ² or more, and particularly preferably 110/mm ² or more. Within such a range, it is possible to obtain a resin foam that preferably has flexibility and is excellent in light-shielding properties and punchability. In addition, the higher the bubble number density, the easier it is to store energy when compressed, and a resin foam having excellent compression recovery can be obtained. The upper limit of the cell number density of the resin foam is preferably 400 cells/mm ² , more preferably 200 cells/mm ² , still more preferably 150 cells/mm ² . The cell number density of the resin foam is the number density in the cross section of cells observed in a randomly selected cross section of the resin foam, and can be obtained by image analysis of the cross section of the resin foam.

The 50% compressive load of the resin foam is preferably 20 N/cm ² or less, more preferably 10 N/cm ² or less, still more preferably 8 N/cm ² or less, still more preferably 5 N/cm ² . or less, and particularly preferably 3 N/cm ² or less. Within such a range, it is possible to obtain a resin foam that preferably has flexibility and is excellent in stamping workability. The lower limit of the 50% compressive load of the resin foam is, for example, 0.5 N/cm ² . The 50% compressive load of the resin foam is the stress (N) when the resin foam is compressed to a compressibility of 50%, converted per unit area (1 cm ² ).

The impact absorption of the resin foam is preferably 20% or more, more preferably 27% or more, still more preferably 30% or more, particularly preferably 35% or more, and most preferably 40%. That's it. Impact absorption is measured as follows.
A test sample was formed by placing a resin foam, double-sided tape (product number: No. 5603W, manufactured by Nitto Denko), and PET film (product number: Diafoil MRF75, manufactured by Mitsubishi Plastics) in this order on the impact force sensor. A 66-g iron ball is dropped onto the specimen from a height of 50 cm above the PET film, and the impact force F1 is measured.
・Furthermore, the impact force F0 of the blank is measured by dropping the iron ball directly onto the impact force sensor as described above.
・From F1 and F0, calculate the impact absorption (%) by the formula (F0-F1)/F0×100.

Any appropriate shape can be adopted as the shape of the resin foam according to the purpose. Such a shape is typically sheet-like.

The resin foam may have a heat-melting layer on one side or both sides. A resin foam having a hot-melt layer is produced by, for example, using a pair of heating rolls heated to a melting temperature of the resin composition constituting the resin foam (or a precursor of the resin foam ( It can be obtained by rolling the foamed structure)).

The resin foam can be formed by any suitable method as long as the effects of the present invention are not impaired. Such a method typically includes a method of foaming a resin composition containing a resin material (polymer).

A-1. Resin Composition The resin foam of the present invention can typically be obtained by foaming a resin composition. The resin composition includes any suitable resin material (polymer). In one embodiment, a non-crosslinkable resin composition is used. A non-crosslinkable resin composition is suitably used in the method for forming a resin foam, which will be described later.

Examples of the polymer include acrylic resins, silicone resins, urethane resins, polyolefin resins, ester resins, and rubber resins. The above polymers may be used singly or in combination of two or more.

The polymer content is preferably 30 parts by weight to 95 parts by weight, more preferably 35 parts by weight to 90 parts by weight, and still more preferably 40 parts by weight to 80 parts by weight with respect to 100 parts by weight of the resin composition. parts, particularly preferably 40 to 60 parts by weight. Within such a range, it is possible to obtain a resin foam that is more excellent in flexibility and stress dispersibility.

In one embodiment, a polyolefin resin is used as the polymer.

The content of the polyolefin resin is preferably 50 parts by weight to 100 parts by weight, more preferably 70 parts by weight to 100 parts by weight, and still more preferably 90 parts by weight to 100 parts by weight, with respect to 100 parts by weight of the polymer. parts by weight, particularly preferably 95 to 100 parts by weight, most preferably 100 parts by weight.

The polyolefin-based resin preferably includes at least one selected from the group consisting of polyolefin and polyolefin-based elastomer, and more preferably, polyolefin and polyolefin-based elastomer are used in combination. Each of polyolefin and polyolefin elastomer may be used alone or in combination of two or more. In this specification, the term "polyolefin" does not include "polyolefin elastomer".

When polyolefin and polyolefin elastomer are used together as polyolefin resin, the weight ratio of polyolefin and polyolefin elastomer (polyolefin/polyolefin elastomer) is preferably 1/99 to 99/1, more preferably 10/90 to 10/90. 90/10, more preferably 20/80 to 80/20, particularly preferably 30/70 to 70/30. In one embodiment, the weight ratio of polyolefin to polyolefin elastomer (polyolefin/polyolefin elastomer) is preferably 25/75 to 75/25, more preferably 35/65 to 65/35. Within such a range, the resin has excellent compression recovery, suppresses shape change (especially thickness change) before and after punching, has appropriate strength, and has excellent punching workability. A foam can be obtained.

Any appropriate polyolefin can be adopted as the polyolefin as long as it does not impair the effects of the present invention. Examples of such polyolefins include linear polyolefins and branched (having branched chains) polyolefins. In one embodiment, a branched polyolefin is used as the polyolefin resin. In this embodiment, as the polyolefin, only branched polyolefin may be used, or branched polyolefin and linear polyolefin may be used in combination. By using a branched polyolefin, a resin foam having a small average cell diameter and excellent impact resistance can be obtained. The content of the branched polyolefin is preferably 30 to 100 parts by weight, more preferably 50 to 80 parts by weight, per 100 parts by weight of the polyolefin.

Examples of the above polyolefins include polymers containing structural units derived from α-olefins. The polyolefin may be composed only of structural units derived from α-olefins, or may be composed of structural units derived from α-olefins and structural units derived from monomers other than α-olefins. When the polyolefin is a copolymer, any appropriate copolymerization form can be adopted as its copolymerization form. Examples include random copolymers and block copolymers.

Examples of α-olefins that can constitute polyolefins include α-olefins having 2 to 8 (preferably 2 to 6, more preferably 2 to 4) carbon atoms (e.g., ethylene, propylene, 1-butene, 1-pentene, , 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, etc.) are preferred. The α-olefin may be of only one type, or may be of two or more types.

Examples of monomers other than α-olefins that constitute polyolefins include ethylenically unsaturated monomers such as vinyl acetate, acrylic acid, acrylic acid esters, methacrylic acid, methacrylic acid esters, and vinyl alcohol. Monomers other than the α-olefin may be of only one type, or may be of two or more types.

Specific examples of polyolefins include low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, polypropylene (propylene homopolymer), copolymers of ethylene and propylene, and ethylene and other than ethylene. copolymers with α-olefins, copolymers of propylene and α-olefins other than propylene, copolymers of ethylene and propylene with α-olefins other than ethylene and propylene, propylene and ethylenically unsaturated monomers and a copolymer with a polymer.

In one embodiment, a polypropylene-based polymer having structural units derived from propylene is used as the polyolefin. Examples of polypropylene-based polymers include polypropylene (propylene homopolymer), copolymers of ethylene and propylene, copolymers of propylene and α-olefins other than propylene, and the like, and preferably polypropylene (propylene homopolymer ). The polypropylene-based polymer may be used alone or in combination of two or more.

The melt flow rate (MFR) of the polyolefin at a temperature of 230° C. is preferably 0.25 g/10 minutes to 10 g/10 minutes, more preferably 0.3 g/10 minutes, in terms of being able to further express the effects of the present invention. min to 6 g/10 min, more preferably 0.35 g/10 min to 5 g/10 min, particularly preferably 0.35 g/10 min to 1 g/10 min, most preferably 0.35 g/10 min. 10 minutes to 0.6 g/10 minutes. In this specification, the melt flow rate (MFR) refers to the MFR measured at a temperature of 230° C. and a load of 2.16 kgf (21.2 N) based on ISO1133 (JIS-K-7210). . In one embodiment, the melt flow rate of the polyolefin that makes up the resin foam controls the die swell ratio and shear viscosity of the resin.

The weight average molecular weight of the polyolefin is preferably 50,000 to 120,000, more preferably 55,000 to 110,000, still more preferably 60,000 to 100,000. Within such a range, the die swell ratio and shear viscosity of the resin can be preferably adjusted. Further, the molecular weight distribution (weight average molecular weight/number average molecular weight) of the polyolefin is preferably 7-10, more preferably 6-9. Within such a range, the die swell ratio and shear viscosity of the resin can be preferably adjusted.
The weight average molecular weight and number average molecular weight can be determined by gel permeation chromatography (solvent: tetrahydrofuran, polystyrene conversion).

Commercially available polyolefins may be used, for example, "E110G" (manufactured by Prime Polymer Co., Ltd.), "EA9" (manufactured by Japan Polypropylene Corporation), "EA9FT" (manufactured by Japan Polypropylene Corporation), "E- 185G" (manufactured by Prime Polymer Co., Ltd.), "WB140HMS" (manufactured by Borealis), and "WB135HMS" (manufactured by Borealis).

Any appropriate polyolefin elastomer can be adopted as the polyolefin elastomer as long as it does not impair the effects of the present invention. Examples of such polyolefin-based elastomers include ethylene-propylene copolymers, ethylene-propylene-diene copolymers, ethylene-vinyl acetate copolymers, polybutene, polyisobutylene, chlorinated polyethylene, polyolefin components and rubber components. So-called non-crosslinked thermoplastic olefin elastomers (TPO), such as elastomers in which polyolefin components and rubber components are physically dispersed, elastomers having a structure in which a polyolefin component and a rubber component are microphase-separated; resin component A (olefin A mixture containing system resin component A) and domain-forming rubber component B is dynamically heat-treated in the presence of a cross-linking agent. dynamically crosslinked thermoplastic olefin elastomer (TPV), which is a multiphase polymer having a sea-island structure in which is finely dispersed as domains (island phases);

The polyolefin elastomer preferably contains a rubber component. Examples of such rubber components include JP-A-08-302111, JP-A-2010-241934, JP-A-2008-024882, JP-A-2000-007858, JP-A-2006-052277, and JP-A-2006-052277. 2012-072306, JP-A-2012-057068, JP-A-2010-241897, JP-A-2009-067969, Table No. 03/002654, and the like.

Specific examples of elastomers having a structure in which a polyolefin component and an olefin-based rubber component are microphase-separated include elastomers composed of polypropylene resin (PP) and ethylene-propylene rubber (EPM), and polypropylene resin (PP). Examples thereof include elastomers made of ethylene-propylene-diene rubber (EPDM). The weight ratio of the polyolefin component to the olefin rubber component (polyolefin component/olefin rubber) is preferably 90/10 to 10/90, more preferably 80/20 to 20/80.

A dynamically crosslinked thermoplastic olefin elastomer (TPV) generally has a higher elastic modulus and a smaller compression set than a non-crosslinked thermoplastic olefin elastomer (TPO). Thereby, the recoverability is good, and excellent recoverability can be exhibited when a resin foam is formed.

The dynamic cross-linking type thermoplastic olefin elastomer (TPV) is, as described above, a mixture containing a matrix-forming resin component A (olefin-based resin component A) and a domain-forming rubber component B, and a cross-linking agent. It is a multiphase polymer having a sea-island structure in which crosslinked rubber particles are finely dispersed as domains (island phases) in resin component A, which is a matrix (sea phase), obtained by dynamic heat treatment in the presence of .

Examples of dynamically crosslinked thermoplastic olefin-based elastomers (TPV) include, for example, JP-A-2000-007858, JP-A-2006-052277, JP-A-2012-072306, JP-A-2012-057068, Examples thereof include those described in JP-A-2010-241897, JP-A-2009-067969, Table No. 03/002654, and the like.

As the dynamic cross-linking type thermoplastic olefin elastomer (TPV), commercially available products may be used. (manufactured by Toyobo Co., Ltd.).

The melt flow rate (MFR) of the polyolefin elastomer at a temperature of 230° C. is preferably 1.5 g/10 minutes to 25 g/10 minutes, more preferably 2 g/10 minutes to 20 g/10 minutes, and still more preferably 2 g/10 minutes to 15 g/10 minutes. In one embodiment, the die swell ratio and shear viscosity of the resin are controlled by the melt flow rate of the polyolefin elastomer that constitutes the resin foam.

In one embodiment, two or more polyolefin-based elastomers having different melt flow rates (MFR) at a temperature of 230°C within the above range are used in combination. In this case, a polyolefin elastomer (low MFR polyolefin elastomer) and a melt flow rate (MFR) at a temperature of 230° C. is preferably 8 g/10 min to 25 g/10 min (more preferably 9 g/10 min to 20 g/10 min, still more preferably 10 g/10 min to 20 g/10 min) polyolefin-based elastomer (high MFR polyolefin-based elastomer). By doing so, the melt tension of the polyolefin elastomer is preferably adjusted, and as a result, the effect of the present invention becomes remarkable.

The compounding ratio of the low MFR polyolefin elastomer to the high MFR polyolefin elastomer (low MFR polyolefin elastomer/high MFR polyolefin elastomer; weight ratio) is preferably 1.5 to 5, more preferably 1.8. ~3.5, particularly preferably 2-3. Within such a range, the melt tension of the polyolefin elastomer is preferably adjusted, and as a result, the effect of the present invention becomes remarkable.

The melt tension (190°C, at break) of the polyolefin elastomer is preferably less than 10 cN, more preferably 5 cN to 9.5 cN. In one embodiment, the die swell ratio and shear viscosity of the resin are controlled by the melt tension of the polyolefin elastomer forming the resin foam.

The JIS A hardness of the polyolefin elastomer is preferably 30° to 95°, more preferably 35° to 90°, still more preferably 40° to 88°, and particularly preferably 45° to 85°. Yes, most preferably between 50° and 83°. JIS A hardness is measured based on ISO7619 (JIS K6253).

In one embodiment, the resin foam (that is, the resin composition) may further contain a filler. By containing a filler, it is possible to form a resin foam that requires a large amount of energy to deform the cell walls, and the resin foam exhibits excellent impact absorption. In addition, by including a filler, it is possible to form a fine and uniform cell structure, which is advantageous in that excellent impact absorption can be exhibited. Only one filler may be used alone, or two or more fillers may be used in combination. In one embodiment, a black material is used as the filler. For example, by using carbon particles, not only the above-mentioned impact absorption property and bubble uniformity effect but also the effect of shielding light is preferably exhibited.

The content of the filler is preferably 5 parts by weight to 150 parts by weight, preferably 10 parts by weight to 150 parts by weight, more preferably 30 parts by weight, with respect to 100 parts by weight of the polymer constituting the resin foam. It is from 50 parts by weight to 130 parts by weight, more preferably from 50 parts by weight to 100 parts by weight. With such a range, the above effect becomes remarkable. When carbon is used as the filler, the content of the carbon is preferably 5 parts by weight to 25 parts by weight, more preferably 7 parts by weight to 20 parts by weight, with respect to 100 parts by weight of the polymer constituting the resin foam. parts by weight, more preferably 10 to 15 parts by weight. With such a range, the above effect becomes remarkable.

In one embodiment, the filler is inorganic. Materials constituting inorganic fillers include, for example, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, and boric acid. Aluminum whiskers, silicon nitride, boron nitride, crystalline silica, amorphous silica, metals (eg, gold, silver, copper, aluminum, nickel), carbon, graphite and the like.

In one embodiment, the filler is organic. Examples of materials constituting the organic filler include polymethyl methacrylate (PMMA), polyimide, polyamideimide, polyetheretherketone, polyetherimide, and polyesterimide.

A flame retardant may be used as the filler. Examples of flame retardants include brominated flame retardants, chlorine flame retardants, phosphorus flame retardants, and antimony flame retardants. From the viewpoint of safety, non-halogen-nonantimony flame retardants are preferably used.

Examples of non-halogen-non-antimony flame retardants include compounds containing aluminum, magnesium, calcium, nickel, cobalt, tin, zinc, copper, iron, titanium, boron, and the like. Examples of such compounds (inorganic compounds) include hydrated metal compounds such as aluminum hydroxide, magnesium hydroxide, magnesium oxide/nickel oxide hydrate, and magnesium oxide/zinc oxide hydrate. .

Any appropriate surface treatment may be applied to the filler. Examples of surface treatment include silane coupling treatment and stearic acid treatment.

The bulk density of the filler is preferably 0.8 g/cm ³ or less, more preferably 0.6 g/cm ³ or less, still more preferably 0.4 g/cm ³ or less, particularly It is preferably 0.3 g/cm ³ or less. Within such a range, the filler can be contained with good dispersibility, and the effect of adding the filler can be sufficiently exhibited while reducing the content of the filler. A resin foam with a low filler content is advantageous in that it is highly foamed, flexible, stress-dispersible, and has excellent appearance. The lower limit of bulk density of the filler is, for example, 0.01 g/cm ³ , preferably 0.05 g/cm ³ , more preferably 0.1 g/cm ³ .

The number average particle size (primary particle size) of the filler is preferably 10 μm or less, more preferably 5 μm or less, more preferably 3 μm or less, and even more preferably 1 μm or less. Within such a range, the filler can be contained with good dispersibility and a uniform cell structure can be formed. As a result, a resin foam having excellent stress dispersibility and appearance can be obtained. When carbon is used as the filler, the number average particle size (primary particle size) of carbon is preferably 10 µm or less, more preferably 5 µm or less, and still more preferably 0.8 µm or less. Within such a range, the filler can be contained with good dispersibility, and excellent light-shielding properties can be exhibited. The lower limit of the number average particle size of the filler is, for example, 0.1 μm. The number average particle diameter of the filler is measured using a particle size distribution analyzer (Micrtrac II, Microtrac Bell Co., Ltd.) using a suspension prepared by mixing 1 g of the filler with 100 g of water at 25° C. as a sample. can do.

The specific surface area of the filler is preferably 2 m ² /g or more, more preferably 4 m ² /g or more, still more preferably 6 m ² /g or more. Within such a range, the filler can be contained with good dispersibility and a uniform cell structure can be formed. As a result, a resin foam having excellent stress dispersibility and appearance can be obtained. The upper limit of the specific surface area of the filler is, for example, 20 m ² /g. The specific surface area of the filler can be measured by the BET method, that is, molecules having a known adsorption area are adsorbed on the surface of the filler at a low temperature using liquid nitrogen, and the adsorption amount is measured.

The resin composition may contain any appropriate other component within a range that does not impair the effects of the present invention. Only one such component may be used, or two or more components may be used. Such other components include, for example, rubber, resins other than polymers blended as resin materials, softeners, aliphatic compounds, anti-aging agents, antioxidants, light stabilizers, weathering agents, and UV absorbers. agent, dispersant, plasticizer, carbon, antistatic agent, surfactant, cross-linking agent, thickener, rust inhibitor, silicone compound, tension modifier, shrinkage inhibitor, fluidity modifier, gelling agents, curing agents, reinforcing agents, foaming agents, foam nucleating agents, coloring agents (pigments, dyes, etc.), pH adjusters, solvents (organic solvents), thermal polymerization initiators, photopolymerization initiators, lubricants, crystal nucleating agents, Crystallization accelerators, vulcanizing agents, surface treatment agents, dispersing aids and the like. In one embodiment, a resin composition is used that does not contain a crosslinker.

A-2. Formation of Resin Foam The resin foam of the present invention is typically obtained by foaming a resin composition. As the method of foaming (method of forming cells), a method commonly used for foam molding, such as a physical method or a chemical method, can be employed. That is, the resin foam may typically be a foam formed by a physical method (physical foam) or a foam formed by a chemical method (chemical foam). foam). Physical methods generally involve dispersing a gaseous component such as air or nitrogen in a polymer solution and mechanically mixing to form cells (mechanical foam). The chemical method is generally a method in which cells are formed by gas generated by thermal decomposition of a foaming agent added to a polymer base to obtain a foam.

The resin composition to be subjected to foam molding is, for example, the constituent components are mixed with any suitable melt-kneading device, such as an open mixing roll, a non-open Banbury mixer, a single-screw extruder, a twin-screw extruder, a continuous type It may be prepared by mixing using any appropriate means such as a kneader, a pressure kneader, and the like.

<Embodiment 1 for forming a resin foam>
As one embodiment 1 for forming a resin foam, for example, an emulsion resin composition (emulsion containing a resin material (polymer), etc.) is mechanically foamed to foam the resin (step A). Forms that form foams are included. The foaming device includes, for example, a high-speed shearing device, a vibrating device, and a pressurized gas discharging device. Among these foaming apparatuses, a high-speed shearing apparatus is preferable from the viewpoint of miniaturization of the bubble diameter and production of a large volume. This one embodiment of forming a resin foam is applicable to forming from any resin composition.

The solid content concentration of the emulsion is preferably higher from the viewpoint of film-forming properties. The solid content concentration of the emulsion is preferably 30% by weight or more, more preferably 40% by weight or more, and still more preferably 50% by weight or more.

　Bubbles generated by mechanical stirring are gas trapped in the emulsion. As the gas, any appropriate gas can be adopted as long as it is inert to the emulsion, as long as it does not impair the effects of the present invention. Such gases include, for example, air, nitrogen, carbon dioxide, and the like.

The resin foam of the present invention can be obtained by applying the emulsion resin composition foamed by the above method (cell-containing emulsion resin composition) onto a substrate and drying it (step B). can. Examples of the substrate include a release-treated plastic film (release-treated polyethylene terephthalate film, etc.), a plastic film (polyethylene terephthalate film, etc.), and the like.

In step B, any appropriate method can be adopted as the coating method and drying method as long as the effects of the present invention are not impaired. Step B comprises a preliminary drying step B1 of drying the bubble-containing emulsion resin composition applied on the base material at 50° C. or more and less than 125° C., and a main drying step B2 of further drying at 125° C. or more and 200° C. or less. preferably.

By providing the preliminary drying step B1 and the main drying step B2, it is possible to prevent coalescence of air bubbles and bursting of air bubbles due to a rapid temperature rise. In particular, with a foamed sheet having a small thickness, the air bubbles coalesce and burst due to a rapid rise in temperature, so the provision of the pre-drying step B1 is of great significance. The temperature in the preliminary drying step B1 is preferably 50°C to 100°C. The duration of the preliminary drying step B1 is preferably 0.5 to 30 minutes, more preferably 1 to 15 minutes. The temperature in the main drying step B2 is preferably 130°C to 180°C or less, more preferably 130°C to 160°C. The time of the main drying step B2 is preferably 0.5 to 30 minutes, more preferably 1 to 15 minutes.

<Embodiment 2 for forming a resin foam>
As one embodiment 2 of forming a resin foam, there is a form in which a foam is formed by foaming a resin composition with a foaming agent. As the foaming agent, those commonly used in foam molding can be used, and from the viewpoint of environmental protection and low contamination of the object to be foamed, it is preferable to use a high-pressure inert gas.

Any appropriate inert gas can be adopted as the inert gas as long as it is inert to the resin composition and can be impregnated. Examples of such inert gas include carbon dioxide, nitrogen gas, and air. These gases may be mixed and used. Among these, carbon dioxide is preferable from the viewpoint of a large impregnation amount to the resin material (polymer) and a high impregnation speed.

The inert gas is preferably in a supercritical state. That is, it is particularly preferable to use carbon dioxide in a supercritical state. In the supercritical state, the solubility of the inert gas in the resin composition increases, and it is possible to mix the inert gas at a high concentration. More nuclei are generated, and the density of the bubbles formed by the growth of the bubble nuclei becomes higher than in other states even if the porosity is the same, so fine bubbles can be obtained. Carbon dioxide has a critical temperature of 31° C. and a critical pressure of 7.4 MPa.

Methods for forming a foam by impregnating a resin composition with an inert gas at high pressure include, for example, a gas impregnation step of impregnating a resin composition containing a resin material (polymer) with an inert gas under high pressure; Examples include a method of forming through a depressurization step in which the pressure is lowered after the step to foam the resin material (polymer) and, if necessary, a heating step in which bubbles are grown by heating. In this case, a preformed unfoamed molded article may be impregnated with an inert gas, or the molten resin composition may be impregnated with an inert gas under pressure and then subjected to molding when the pressure is reduced. may These steps may be carried out by either a batch system or a continuous system. That is, a resin composition is preliminarily molded into an appropriate shape such as a sheet to form an unfoamed resin molded body, and then the unfoamed resin molded body is impregnated with high-pressure gas and expanded by releasing the pressure. It may be a batch system, or a continuous system in which the resin composition is kneaded under pressure with a high-pressure gas, molded and at the same time the pressure is released, and molding and foaming are performed simultaneously.

Below is an example of producing foam in a batch method. For example, a resin sheet for foam molding is produced by extruding the resin composition using an extruder such as a single-screw extruder or a twin-screw extruder. Alternatively, the resin composition may be uniformly kneaded using a kneader equipped with blades such as a roller, a cam, a kneader, or a Banbury type, and then pressed to a predetermined thickness using a hot plate press or the like. A non-foamed resin molding is produced by the above. The unfoamed resin molded article thus obtained is placed in a high-pressure vessel, and a high-pressure inert gas (such as carbon dioxide in a supercritical state) is injected to impregnate the unfoamed resin molded article with the inert gas. When the inert gas is sufficiently impregnated, the pressure is released (usually to atmospheric pressure) to generate bubble nuclei in the resin. The bubble nuclei may be grown at room temperature as they are, or may be grown by heating in some cases. As a heating method, a known or commonly used method such as a water bath, an oil bath, a hot roll, a hot air oven, far infrared rays, near infrared rays, or microwaves can be used. After the cells are grown in this manner, the foam is rapidly cooled with cold water or the like to fix the shape, thereby obtaining a foam. The unfoamed resin molding to be foamed is not limited to a sheet-like article, and various shapes can be used depending on the application. In addition, the unfoamed resin molded article to be foamed can be produced by extrusion molding, press molding, or other molding methods such as injection molding.

An example of continuous production of foam is shown below. For example, while kneading the resin composition using an extruder such as a single-screw extruder or a twin-screw extruder, a high-pressure gas (especially an inert gas, further carbon dioxide) is injected (introduced), and the In the kneading impregnation process, the resin composition is impregnated with high-pressure gas, and the pressure is released by extruding the resin composition through a die or the like provided at the tip of the extruder (usually to atmospheric pressure), and molding and foaming are performed at the same time. Foam molding is performed by the molding depressurization step performed. In addition, in the case of continuous foam molding, a heating step may be provided, if necessary, to grow air bubbles by heating. After the bubbles are grown in this way, if necessary, they may be rapidly cooled with cold water or the like to fix the shape. Also, the high-pressure gas may be introduced continuously or discontinuously. Furthermore, for example, an extruder or an injection molding machine can be used in the kneading impregnation step and the molding depressurization step. Any suitable heating method such as water bath, oil bath, hot roll, hot air oven, far-infrared rays, near-infrared rays, and microwaves can be used as a heating method for growing bubble nuclei. Any appropriate shape can be adopted as the shape of the foam. Such shapes include, for example, a sheet shape, prismatic shape, cylindrical shape, irregular shape, and the like.

The amount of gas to be mixed when foam-molding the resin composition is preferably 2% to 10% by weight with respect to the total amount of the resin composition, in that a highly foamed resin foam can be obtained. Yes, more preferably 2.5 wt % to 8 wt %, still more preferably 3 wt % to 6 wt %.

The pressure when the resin composition is impregnated with the inert gas can be appropriately selected in consideration of operability and the like. Such pressure is, for example, preferably 6 MPa or higher (eg, 6 MPa to 100 MPa), more preferably 8 MPa or higher (eg, 8 MPa to 50 MPa). When using supercritical carbon dioxide, the pressure is preferably 7.4 MPa or more from the viewpoint of maintaining the supercritical state of carbon dioxide. If the pressure is lower than 6 MPa, the cell growth during foaming will be significant, and the cell diameter will become too large, and a preferable average cell diameter (average cell diameter) may not be obtained. This is because when the pressure is low, the amount of gas impregnated is relatively small compared to when the pressure is high, and the bubble nucleus formation rate decreases, resulting in a decrease in the number of bubble nuclei formed. This is because the bubble diameter becomes extremely large. In addition, in a pressure range lower than 6 MPa, even a slight change in the impregnation pressure significantly changes the bubble diameter and bubble density, making it difficult to control the bubble diameter and bubble density.

The temperature in the gas impregnation process varies depending on the inert gas used and the type of components in the resin composition, and can be selected within a wide range. When operability and the like are considered, the temperature is preferably 10°C to 350°C. The impregnation temperature for impregnating an unfoamed molded article with an inert gas is preferably 10° C. to 250° C., more preferably 40° C. to 230° C. in a batch system. Further, the impregnation temperature when foaming and molding are simultaneously performed by extruding a molten polymer impregnated with a gas is preferably 60° C. to 350° C. in a continuous system. When carbon dioxide is used as the inert gas, the temperature during impregnation is preferably 32° C. or higher, more preferably 40° C. or higher, in order to maintain a supercritical state.

In the decompression step, the decompression speed is preferably 5 MPa/sec to 300 MPa/sec in order to obtain uniform microbubbles.

The heating temperature in the heating step is preferably 40°C to 250°C, more preferably 60°C to 250°C.

In one embodiment, after obtaining a foamed structure through a predetermined process (for example, after obtaining a resin foam by the method of <Embodiment 1> or <Embodiment 2>), the foamed structure is formed into a thin film. Then, it is roll-rolled to obtain a resin foam. Through such steps, a resin foam having an appropriately adjusted aspect ratio can be obtained. Moreover, a resin foam having a small thickness (for example, 0.2 mm or less) can be obtained. The hot melt layer may be formed by the roll rolling.

Thinning of the foam structure can be performed using any appropriate slicer. The thickness of the foam structure after thinning is preferably 0.01 mm to 3 mm, more preferably 0.05 mm to 2 mm, even more preferably 0.1 mm to 1 mm, and particularly preferably 0.1 mm to 0.5 mm.

Preferably, the rolls used for the roll rolling are heating rolls. The temperature of the roll is preferably 150°C to 250°C, more preferably 160°C to 230°C.

The rolling rate of the foamed structure (thickness after rolling/thickness before rolling×100) is preferably 80% or less, more preferably 10% to 80%, still more preferably 20% to 75%. , particularly preferably 30% to 75%. Within such a range, a resin foam with an appropriately adjusted aspect ratio can be obtained.

B. Foam Member FIG. 1 is a schematic cross-sectional view of a foam member according to one embodiment. The foam member 100 has a resin foam layer 10 and an adhesive layer 20 arranged on at least one side of the resin foam layer 10 . The resin foam layer 10 is composed of the above resin foam.

The thickness of the adhesive layer is preferably 5 µm to 300 µm, more preferably 6 µm to 200 µm, more preferably 7 µm to 100 µm, and particularly preferably 8 µm to 50 µm. By setting the thickness of the pressure-sensitive adhesive layer within the above range, the foamed member of the present invention can exhibit excellent impact absorption.

A layer made of any suitable adhesive can be adopted as the adhesive layer. Examples of adhesives constituting the adhesive layer include rubber-based adhesives (synthetic rubber-based adhesives, natural rubber-based adhesives, etc.), urethane-based adhesives, acrylic urethane-based adhesives, acrylic-based adhesives, and silicone-based adhesives. Adhesives, polyester-based adhesives, polyamide-based adhesives, epoxy-based adhesives, vinyl alkyl ether-based adhesives, fluorine-based adhesives, rubber-based adhesives, and the like can be mentioned. The adhesive constituting the adhesive layer is preferably at least one selected from acrylic adhesives, silicone adhesives, and rubber adhesives. Only one type of such adhesive may be used, or two or more types may be used. The pressure-sensitive adhesive layer may be one layer, or two or more layers.

As the adhesive, when classified by adhesive form, for example, emulsion type adhesive, solvent type adhesive, ultraviolet cross-linking (UV cross-linking) adhesive, electron beam cross-linking (EB cross-linking) adhesive, hot melt adhesive agents (hot-melt adhesives) and the like. Only one type of such adhesive may be used, or two or more types may be used.

The water vapor permeability of the pressure-sensitive adhesive layer is preferably 50 (g/(m ² ·24 hours)) or less, more preferably 30 (g/(m ² ·24 hours)) or less, still more preferably 20 (g/(m ² ·24 hours)) or less, particularly preferably 10 (g/(m ² ·24 hours)) or less. If the water vapor permeability of the pressure-sensitive adhesive layer is within the above range, the foam sheet can stabilize impact absorption without being affected by moisture. The water vapor transmission rate can be measured, for example, by a method according to JIS Z 0208 under test conditions of 40° C. and relative humidity of 92%.

The adhesive that constitutes the adhesive layer may contain any appropriate other component within a range that does not impair the effects of the present invention. Other components include, for example, other polymer components, softeners, antioxidants, curing agents, plasticizers, fillers, antioxidants, thermal polymerization initiators, photopolymerization initiators, ultraviolet absorbers, and light stabilizers. , coloring agents (pigments, dyes, etc.), solvents (organic solvents), surfactants (e.g., ionic surfactants, silicone-based surfactants, fluorine-based surfactants, etc.), cross-linking agents (e.g., polyisocyanate-based cross-linking agents, silicone-based cross-linking agents, epoxy-based cross-linking agents, alkyl-etherified melamine-based cross-linking agents, etc.). A thermal polymerization initiator and a photopolymerization initiator can be included in the material for forming the polymer component.

The foam member can be manufactured by any appropriate method. The foamed member is produced, for example, by laminating a foamed resin layer and a pressure-sensitive adhesive layer, or by laminating a material for forming the pressure-sensitive adhesive layer and a foamed resin layer, and then forming a pressure-sensitive adhesive layer by a curing reaction or the like. methods and the like.

The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The tests and evaluation methods used in Examples and the like are as follows. "Parts" means "parts by weight" unless otherwise specified, and "%" means "% by weight" unless otherwise specified.

<Evaluation method>
(1) Apparent density Y
The density (apparent density) of the resin foam was calculated as follows. The resin foams obtained in Examples and Comparative Examples were punched out into 20 mm×20 mm size test pieces, and the dimensions of the test pieces were measured with vernier calipers. Next, the weight of the test piece was measured with an electronic balance. Then, it was calculated by the following formula.
Apparent density (g/cm ³ ) = weight of test piece/volume of test piece

(2) 50% Compressive Load Measured according to the method for measuring compression hardness of resin foam described in JIS K 6767. Specifically, the stress (N ) was converted to a unit area (1 cm ² ) to obtain a 50% compressive load (N/cm ² ).

(3) Average cell diameter (average cell diameter), coefficient of variation of cell diameter (cell diameter) The resin foam is treated with a razor blade in the TD (direction perpendicular to the flow direction), and the main surface of the resin foam Cut in the vertical direction (thickness direction), use a digital microscope (trade name "VHX-500", manufactured by Keyence Corporation) as a measuring instrument, capture the cut surface image of the resin foam, and use the measuring instrument The number average bubble diameter (average cell diameter) (μm) was determined by image analysis using analysis software. The number of bubbles in the captured enlarged image was about 400. In addition, the standard deviation was calculated from all the cell diameter data, and the coefficient of variation was calculated using the following formula.
Variation coefficient = standard deviation / average bubble diameter (average cell diameter)

(4) Bubble rate (cell rate)
The measurement was performed in an environment with a temperature of 23°C and a humidity of 50%. A 100 mm × 100 mm punching blade (processing blade (trade name “NCA07”, thickness 0.7 mm, cutting edge angle 43°, manufactured by Nakayama Co., Ltd.)) is used to punch out the resin foams obtained in Examples and Comparative Examples, The dimensions of the punched samples were measured. Also, the thickness was measured with a 1/100 dial gauge having a measuring terminal diameter (φ) of 20 mm. From these values, the volumes of the resin foams obtained in Examples and Comparative Examples were calculated. Next, the weights of the resin foams obtained in Examples and Comparative Examples were measured with a balance with a minimum scale of 0.01 g or more. From these values, the void ratio (cell ratio) of the resin foams obtained in Examples and Comparative Examples was calculated.

(5) Open cell rate Under an environment of temperature 23 ° C. and humidity 50%, the resin foam is submerged in water, then weighed, then sufficiently dried in an oven at 80 ° C., and weighed again. was measured. From the water content obtained by the weight measurement, the volume of the open cells was determined, and the volume ratio of the open cells to the volume of the resin foam (open cell ratio) was determined.

(6) Cell Number Density The resin foam was cut with a razor blade in the TD (direction orthogonal to the flow direction) and in the direction (thickness direction) perpendicular to the main surface of the resin foam.
Using a digital microscope (trade name "VHX-500", manufactured by Keyence Corporation) as a measuring instrument, capturing an image of the cut surface of the resin foam and analyzing the image using the analysis software of the measuring instrument, the unit The number of air bubbles per area [mm ² ] was measured.

(7) Thickness of cell wall Using a razor blade, the resin foam is cut in TD (direction perpendicular to the flow direction) and perpendicular to the main surface of the resin foam (thickness direction), and measured. Using a digital microscope (trade name "VHX-500", manufactured by Keyence Corporation) as a device, an enlarged image of the bubble part of the resin foam is captured, and the image is analyzed using the analysis software of the same measuring device. , the thickness (μm) of the bubble wall (cell wall) was determined. The number of bubbles in the captured enlarged image was about 400.

(8) Light transmittance X in bulk state after pressing
A resin foam was sandwiched between aluminum plates (thickness 0.5 mm), a spacer of about 0.03 mm thick was provided, and pressed while applying a temperature above the melting point to obtain a bulk sheet with a thickness of 0.03 mm. The sheet was measured for light transmittance at a wavelength of 550 nm using an ultraviolet/visible/near-infrared spectrophotometer (manufactured by Shimadzu Corporation: SolidSpec-3700) as a measuring instrument.
In addition, in the case of a resin foam (Example 7) that is less than a resin foam with a thickness of 1.0 mm, three layers of the resin foam are stacked and then pressed to form a sheet with a thickness of 0.03 mm in a bulk state. Obtained.

(9) Thickness recovery rate (instantaneous recovery rate)
A load of 1000 g/cm ² was applied to the resin foam and maintained for 120 seconds, and the compression was released. After 0.5 seconds, the thickness) was measured. The thickness recovery rate (instantaneous recovery rate) is obtained by the following formula from the "thickness 0.5 seconds after releasing the compressed state" and the thickness (initial thickness) of the resin foam before the load is applied. rice field.
Thickness recovery rate (%) = {(thickness 0.5 seconds after releasing the compressed state) / (initial thickness)} x 100

(10) Punching workability (10 mm × 10 mm)
Using a mold (two processing blades (trade name “NCA07”, thickness 0.7 mm, blade edge angle 43°, distance between two processing blades 10 mm, manufactured by Nakayama Co., Ltd.)), Punching is performed in the MD direction (flow direction) and TD direction (perpendicular to the flow direction) to obtain a size of 10 mm x 10 mm. (trade name “VHX-2000” manufactured by Keyence Corporation). Using the edge thickness measured from the image and the thickness before punching, the thickness recovery rate after processing was measured by the following formula. The larger the thickness recovery rate, the smaller the change in shape due to punching, and the better the punching workability.
Thickness recovery rate after processing (%) = 100 × (1 - (thickness before punching - thickness of edge) / thickness before punching)

(11) Punching workability (1 mm width)
The resin foam is molded using a mold (two processing blades (trade name “NCA07”, thickness 0.7 mm, blade angle 43 °, interval between two processing blades 1 mm, manufactured by Nakayama Co., Ltd.)). Punching is performed in the direction (flow direction) with a distance of 1 mm between the two processing blades and a length of 50 mm, and in the direction (thickness direction) perpendicular to the main surface of the resin foam. "VHX-2000" (manufactured by Keyence Corporation) was used for observation. Using the edge thickness measured from the image and the thickness before punching, the thickness recovery rate after processing was measured by the following formula. The larger the thickness recovery rate, the smaller the change in shape due to punching, and the better the punching workability.
Thickness recovery rate after processing (%) = 100 × (1 - (thickness before punching - thickness of edge) / thickness before punching)

(12) Transmittance of resin foam The resin foam is measured with an ultraviolet/visible/near-infrared spectrophotometer (manufactured by Shimadzu Corporation: SolidSpec-3700), and the light transmittance at a wavelength of 550 nm. was measured.

(13) Die swell ratio A sample ( A resin (size: 5 mm square) that constitutes the resin foam is put in and melted over 7 minutes. After that, the molten product was extruded into a die having a length of 10 mm and a diameter of 1 mmφ at a shear rate of 20 mm / s, and the diameter of the obtained string-shaped molded product was measured with a digital caliper (trade name “CD67-s PM”, Mitutoyo Co., Ltd. (Company), and the die swell ratio was calculated from the following formula. The die swell ratio of the resin was measured before and after foaming.
Die swell ratio = diameter of molding (mm) / diameter of die (mm)

(14) Shear viscosity A sample (resin A resin (size: 5 mm square) that constitutes the foam is added and melted over 7 minutes. Thereafter, the melt was extruded through a die having a length of 10 mm and a diameter of 1 mmφ at a shear rate of 20 mm/s, and the shear viscosity was measured. The shear viscosity of the resin was measured before and after foaming.

[Example 1]
Polypropylene (propylene homopolymer, MFR: 0.4 g/10 min (230°C, load 21.2 N), density: 0.90 g/cm ³ , ethylene content: 0 wt%, propylene content: 100 wt%, weight average Molecular weight: 64500, molecular weight distribution: 8.43) 30 parts by weight, polyolefin elastomer (melt flow rate (MFR): 15 g/10 min, JIS A hardness: 79°) 46 parts by weight, polyolefin elastomer (melt flow rate (MFR ): 2.2 g / 10 min, JIS A hardness: 69 °) 19 parts by weight, magnesium hydroxide (trade name “KISUMA 5P” manufactured by Kyowa Chemical Industry) 10 parts by weight, carbon (trade name “Asahi # 35” Asahi Carbon Co., Ltd. Company) 10 parts by weight and 1 part by weight of stearic acid monoglyceride are kneaded at a temperature of 200 ° C. in a twin-screw kneader manufactured by Japan Steel Works (JSW), extruded into strands, water-cooled and pelletized. molded into The pellets were put into a single-screw extruder manufactured by Japan Steel Works, Ltd., and carbon dioxide gas was injected under an atmosphere of 220° C. and a pressure of 13 MPa (12 MPa after injection). Carbon dioxide gas was injected at a rate of 4.8 parts by weight with respect to 100 parts by weight of the resin. After sufficiently saturating the carbon dioxide gas, it was cooled to a temperature suitable for foaming, and then extruded from a die to obtain a sheet-like resin foam a.
Furthermore, it was thinned using a slicer to obtain a resin foam A having a thickness of 1.0 mm.
The obtained resin foam A was subjected to the above evaluation. Table 1 shows the results.

[Example 2]
Polypropylene (propylene homopolymer, MFR: 0.4 g/10 min (230°C, load 21.2 N), density: 0.90 g/cm ³ , ethylene content: 0 wt%, propylene content: 100 wt%) 35 weight part, polyolefin elastomer (melt flow rate (MFR): 15 g/10 min, JIS A hardness: 79°) 42 parts by weight, polyolefin elastomer (melt flow rate (MFR): 2.2 g/10 min, JIS A hardness: 69 °) 18 parts by weight, 10 parts by weight of magnesium hydroxide (trade name "KISUMA 5P" manufactured by Kyowa Chemical Industry Co., Ltd.), 10 parts by weight of carbon (trade name "Asahi #35" manufactured by Asahi Carbon Co., Ltd.), and 1 weight part of stearic acid monoglyceride The parts were kneaded at a temperature of 200° C. using a twin-screw kneader manufactured by Japan Steel Works (JSW), extruded into strands, cooled with water, and formed into pellets. The pellets were put into a single-screw extruder manufactured by Japan Steel Works, Ltd., and carbon dioxide gas was injected under an atmosphere of 220° C. and a pressure of 13 MPa (12 MPa after injection). Carbon dioxide gas was injected at a rate of 4.8 parts by weight with respect to 100 parts by weight of the resin. After sufficiently saturating the carbon dioxide gas, it was cooled to a temperature suitable for foaming, and then extruded through a die to obtain a sheet-like resin foam b.
Furthermore, it was thinned using a slicer to obtain a resin foam B having a thickness of 1.0 mm.
The obtained resin foam B was subjected to the above evaluation. Table 1 shows the results.

[Example 3]
A resin foam c was obtained in the same manner as in Example 2, except that the injection amount of carbon dioxide gas was 4.5 parts by weight with respect to 100 parts by weight of the resin.
Furthermore, it was thinned using a slicer to obtain a resin foam C having a thickness of 1.0 mm.
The obtained resin foam C was subjected to the above evaluation. Table 1 shows the results.

[Example 4]
A resin foam d was obtained in the same manner as in Example 2, except that the injection amount of carbon dioxide gas was 4.2 parts by weight with respect to 100 parts by weight of the resin.
Furthermore, it was thinned using a slicer to obtain a resin foam D having a thickness of 1.0 mm.
The obtained resin foam D was subjected to the above evaluation. Table 1 shows the results.

[Example 5]
Polypropylene (propylene homopolymer, MFR: 0.4 g/10 min (230° C., load 21.2 N), density: 0.90 g/cm ³ , ethylene content: 0% by weight, propylene content: 100% by weight) 40 weight part, polyolefin elastomer (melt flow rate (MFR): 15 g/10 min, JIS A hardness: 79°) 39 parts by weight, polyolefin elastomer (melt flow rate (MFR): 2.2 g/10 min, JIS A hardness: 69 °) 16 parts by weight, magnesium hydroxide (trade name “KISUMA 5P” manufactured by Kyowa Chemical Industry Co., Ltd.) 10 parts by weight, carbon (trade name “Asahi #35” manufactured by Asahi Carbon Co., Ltd.) 10 parts by weight, and stearic acid monoglyceride 1 weight The parts were kneaded at a temperature of 200° C. using a twin-screw kneader manufactured by Japan Steel Works (JSW), extruded into strands, cooled with water, and formed into pellets. The pellets were put into a single-screw extruder manufactured by Japan Steel Works, Ltd., and carbon dioxide gas was injected under an atmosphere of 220° C. and a pressure of 13 MPa (12 MPa after injection). Carbon dioxide gas was injected at a rate of 4.5 parts by weight with respect to 100 parts by weight of the resin. After sufficiently saturating the carbon dioxide gas, it was cooled to a temperature suitable for foaming, and then extruded through a die to obtain a sheet-like resin foam e.
Furthermore, it was thinned using a slicer to obtain a resin foam E having a thickness of 1.0 mm.
The obtained resin foam E was subjected to the above evaluation. Table 1 shows the results.

[Example 6]
Polypropylene (propylene homopolymer, MFR: 0.5 g/10 min (230°C, load 21.2 N), density: 0.90 g/cm ³ , ethylene content: 0 wt%, propylene content: 100 wt%, weight average Molecular weight: 54500, molecular weight distribution: 9.83) 40 parts by weight, polyolefin elastomer (melt flow rate (MFR): 15 g/10 min, JIS A hardness: 79°) 39 parts by weight, polyolefin elastomer (melt flow rate (MFR ): 2.2 g / 10 min, JIS A hardness: 69 °) 16 parts by weight, magnesium hydroxide (trade name “KISUMA 5P” manufactured by Kyowa Chemical Industry) 10 parts by weight, carbon (trade name “Asahi #35” Asahi Carbon Co., Ltd. Company) 10 parts by weight and 1 part by weight of stearic acid monoglyceride are kneaded at a temperature of 200 ° C. in a twin-screw kneader manufactured by Japan Steel Works (JSW), extruded into strands, water-cooled and pelletized. molded into The pellets were put into a single-screw extruder manufactured by Japan Steel Works, Ltd., and carbon dioxide gas was injected under an atmosphere of 220° C. and a pressure of 13 MPa (12 MPa after injection). Carbon dioxide gas was injected at a rate of 4.5 parts by weight with respect to 100 parts by weight of the resin. After sufficiently saturating the carbon dioxide gas, it was cooled to a temperature suitable for foaming, and extruded through a die to obtain a sheet-like resin foam f.
Furthermore, it was thinned using a slicer to obtain a resin foam F having a thickness of 1.0 mm.
The obtained resin foam F was subjected to the above evaluation. Table 1 shows the results.

[Example 7]
A resin foam g was obtained in the same manner as in Example 2, except that the injection amount of carbon dioxide gas was 4.2 parts by weight with respect to 100 parts by weight of the resin.
Furthermore, it was thinned using a slicer to obtain a resin foam having a thickness of 0.3 mm. Furthermore, the resin foam is passed through a pair of rolls, one of which is heated to 230 ° C. (the gap between the rolls) to obtain a resin foam E having a thickness of 0.20 mm. rice field. The gap (clearance) between the rolls was set so as to obtain a resin foam G having a thickness of 0.20 mm.
The obtained resin foam G was subjected to the above evaluation. Table 1 shows the results.

[Example 8]
Polypropylene (propylene homopolymer, MFR: 0.4 g/10 min (230°C, load 21.2 N), density: 0.90 g/cm ³ , ethylene content: 0 wt%, propylene content: 100 wt%, weight average Molecular weight: 64500, molecular weight distribution: 8.43) 45 parts by weight, polypropylene (propylene homopolymer, MFR: 0.5 g/10 min (230°C, load 21.2 N), density: 0.90 g/cm ³ , ethylene content: 0% by weight, propylene content: 100% by weight, weight average molecular weight: 54500, molecular weight distribution: 9.83) 20 parts by weight, polyolefin elastomer (melt flow rate (MFR): 15 g/10 min, JIS A hardness: 79 °) 25 parts by weight, polyolefin elastomer (melt flow rate (MFR): 2.2 g/10 min, JIS A hardness: 69 °) 10 parts by weight, magnesium hydroxide (trade name “KISUMA 5P” manufactured by Kyowa Chemical Industry) 120 Parts by weight, 10 parts by weight of carbon (trade name “Asahi #35” manufactured by Asahi Carbon Co., Ltd.), and 1 part by weight of stearic acid monoglyceride are mixed with a twin-screw kneader manufactured by Japan Steel Works (JSW) at 200 ° C. After kneading at temperature, the mixture was extruded into strands, cooled with water, and formed into pellets. The pellets were put into a single-screw extruder manufactured by Japan Steel Works, Ltd., and carbon dioxide gas was injected under an atmosphere of 220° C. and a pressure of 13 MPa (12 MPa after injection). Carbon dioxide gas was injected at a rate of 4.2 parts by weight with respect to 100 parts by weight of the resin. After sufficiently saturating the carbon dioxide gas, it was cooled to a temperature suitable for foaming, and then extruded through a die to obtain a sheet-like resin foam h.
Furthermore, it was thinned using a slicer to obtain a resin foam H having a thickness of 1.0 mm.
The obtained resin foam H was subjected to the above evaluation. Table 1 shows the results.

[Comparative Example 1]
Polypropylene (propylene homopolymer, MFR: 0.4 g/10 min (230°C, load 21.2 N), density: 0.90 g/cm ³ , ethylene content: 0 wt%, propylene content: 100 wt%, weight average Molecular weight: 108,000, molecular weight distribution: 4.93) 65 parts by weight, polyolefin elastomer (melt flow rate (MFR): 15 g/10 min, JIS A hardness: 79°) 35 parts by weight, magnesium hydroxide (trade name "KISUMA 5P ” manufactured by Kyowa Chemical Industry Co., Ltd.) 5 parts by weight, carbon (trade name “Asahi #35” manufactured by Asahi Carbon Co., Ltd.) 10 parts by weight, and 1 part by weight of stearic acid monoglyceride are biaxially kneaded by Japan Steel Works (JSW). After kneading at a temperature of 200° C. in a machine, the mixture was extruded into strands, cooled with water, and formed into pellets. The pellets were put into a single-screw extruder manufactured by Japan Steel Works, Ltd., and carbon dioxide gas was injected under an atmosphere of 220° C. and a pressure of 13 MPa (12 MPa after injection). Carbon dioxide gas was injected at a rate of 4.5 parts by weight with respect to 100 parts by weight of the resin. After sufficiently saturating the carbon dioxide gas, it was cooled to a temperature suitable for foaming, and then extruded through a die to obtain a sheet-like resin foam i.
Furthermore, it was thinned using a slicer to obtain a resin foam I having a thickness of 1.0 mm.
The obtained resin foam I was subjected to the above evaluation. Table 1 shows the results.

[Comparative Example 2]
Polypropylene (propylene homopolymer, MFR: 0.4 g/10 min (230°C, load 21.2 N), density: 0.90 g/cm ³ , ethylene content: 0 wt%, propylene content: 100 wt%, weight average Molecular weight: 64,500, molecular weight distribution: 8.43) 45 parts by weight, polyolefin elastomer (melt flow rate (MFR): 15 g/10 min, JIS A hardness: 79°) 55 parts by weight, magnesium hydroxide (trade name "KISUMA 5P ” manufactured by Kyowa Chemical Industry Co., Ltd.) 5 parts by weight, carbon (trade name “Asahi #35” manufactured by Asahi Carbon Co., Ltd.) 10 parts by weight, and 1 part by weight of stearic acid monoglyceride are biaxially kneaded by Japan Steel Works (JSW). After kneading at a temperature of 200° C. in a machine, the mixture was extruded into strands, cooled with water, and formed into pellets. The pellets were put into a single-screw extruder manufactured by Japan Steel Works, Ltd., and carbon dioxide gas was injected under an atmosphere of 220° C. and a pressure of 13 MPa (12 MPa after injection). Carbon dioxide gas was injected at a rate of 4.5 parts by weight with respect to 100 parts by weight of the resin. After sufficiently saturating the carbon dioxide gas, it was cooled to a temperature suitable for foaming, and then extruded through a die to obtain a sheet-like resin foam j.
Furthermore, it was thinned using a slicer to obtain a resin foam J having a thickness of 1.0 mm.
The obtained resin foam J was subjected to the above evaluation. Table 1 shows the results.

[Comparative Example 3]
A resin foam (apparent density: 0.15 g/cm ³ , 50% compression load: 1.0 N/cm ² , thickness: 1.0 mm) containing polyurethane as a main component was prepared. The resin foam was subjected to the above evaluation. Table 1 shows the results.

[Comparative Example 4]
A resin foam containing polyurethane as a main component (apparent density: 0.25 g/cm ³ , 50% compression load: 2.1 N/cm ² , thickness: 1.0 mm) was prepared. The resin foam was subjected to the above evaluation. Table 1 shows the results.

As is clear from Table 1, in the resin foam of the present invention, the light transmittance X and the apparent density Y in the bulk state after pressing satisfy the relationship of the above formula (1), and the instantaneous recovery rate is By being in the specific range, the "transmittance of the resin foam" is low, that is, it has high light-shielding properties and is excellent in punching workability.

The resin foam of the present invention can be suitably used, for example, as a cushioning material for electronic devices.

100 foam member 10 resin foam layer (resin foam)
20 adhesive layer

Claims

A resin foam having a cell structure and an apparent density of 0.03 g/cm 3 or more,
The light transmittance X (%) in the bulk state after pressing and the apparent density Y (g/cm 3 ) satisfy the relationship of the following formula (1),
100Y-4X>3 (1)
The thickness recovery rate after maintaining a load of 1000 g/cm 2 on the resin foam for 120 seconds is 80% or more.
Resin foam.
The resin foam according to claim 1, wherein the light transmittance X in the bulk state after pressing is 2.0% or less.
The resin foam according to Claim 1, wherein the apparent density Y is less than 0.4 g/ cm3 .
The resin foam according to claim 1, which has a cell number density of 30 cells/ mm2 or more.
The resin foam according to claim 1, wherein the coefficient of variation of cell diameter is 0.5 or less.
The resin foam according to claim 1, which has an average cell diameter of 10 μm to 200 μm.
The resin foam according to claim 1, which has a void content of 30% or more.
The resin foam according to claim 1, having a 50% compression load of 20 N/cm 2 or less.
The resin foam according to claim 1, which contains a polyolefin resin.　
The resin foam according to claim 9, wherein the polyolefin resin is a mixture of a polyolefin other than a polyolefin elastomer and a polyolefin elastomer.
The resin foam according to claim 1, which has a heat-melting layer on one side or both sides.
Having a resin foam layer and an adhesive layer disposed on at least one side of the resin foam layer,
The resin foam layer is the resin foam according to claim 1,
foam material.