阅读说明：本技术 聚烯烃系树脂发泡体片及使用其的粘接胶带 (Polyolefin resin foam sheet and adhesive tape using same ) 是由 石田昌也 矢野秀明 于 2020-02-28 设计创作，主要内容包括：本发明的聚烯烃系树脂发泡体片的弯曲弹性模量为150kPa以下,并且在120℃的温度下进行了1小时养护后的面方向的收缩率为5％以下。另一方面,本发明的粘接胶带具备本发明的聚烯烃系树脂发泡体片、和设置在本发明的聚烯烃系树脂发泡体片的至少一面的粘接剂层。由此,可以提供耐热性高,曲面追随性优异的聚烯烃系树脂发泡体片以及使用了该聚烯烃系树脂发泡体片的粘接胶带。(The polyolefin resin foam sheet of the present invention has a flexural modulus of elasticity of 150kPa or less and a shrinkage ratio in the in-plane direction after curing at a temperature of 120 ℃ for 1 hour of 5% or less. On the other hand, the adhesive tape of the present invention includes the polyolefin resin foam sheet of the present invention and an adhesive layer provided on at least one surface of the polyolefin resin foam sheet of the present invention. Thus, a polyolefin resin foam sheet having high heat resistance and excellent curved surface conformability and an adhesive tape using the polyolefin resin foam sheet can be provided.)

1. A polyolefin resin foam sheet having a flexural modulus of 150kPa or less and a high impact strength

The shrinkage rate in the planar direction after curing at a temperature of 120 ℃ for 1 hour is 5% or less.

2. The polyolefin resin foam sheet according to claim 1, wherein the average cell diameter of the cells in the MD direction and the average cell diameter of the cells in the TD direction is 400 μm or less.

3. The polyolefin resin foam sheet according to claim 1 or 2, which is obtained by foaming a resin composition comprising a resin (A) having a propylene-derived structural unit,

the content of the resin (A) in the resin composition is 25 to 95 parts by mass relative to 100 parts by mass of the resin component of the resin composition.

4. The polyolefin resin foam sheet according to claim 3, wherein the resin (A) comprises at least 1 resin selected from the group consisting of polypropylene resins, ethylene-propylene random copolymer rubbers, and olefin thermoplastic elastomers, which have a structural unit derived from propylene.

5. The polyolefin resin foam sheet according to claim 4, wherein the resin (A) comprises the polypropylene resin and the olefin thermoplastic elastomer.

6. The polyolefin resin foam sheet according to claim 4 or 5, wherein the polypropylene resin is random polypropylene.

7. The polyolefin resin foam sheet according to any one of claims 1 to 6, which has a thickness of 0.03 to 1.5 mm.

8. The polyolefin resin foam sheet according to any one of claims 1 to 7, which has an apparent density of 0.05 to 0.6g/cm³。

9. An adhesive tape comprising the polyolefin resin foam sheet according to any one of claims 1 to 8, and an adhesive layer provided on at least one surface of the polyolefin resin foam sheet.

Technical Field

The present invention relates to a polyolefin resin foam sheet and an adhesive tape using the same.

Background

Polyolefin resin foams are generally excellent in flexibility, light weight, impact absorption and thermal insulation properties, and are commonly used as laminates with skin materials, thermal insulation materials, cushioning materials, and the like. Further, the polyolefin resin foam has excellent flexibility and excellent impact absorbability, and therefore is used as a foam tape (foam tape) for fixing electronic devices. For example, polyethylene resins are used as polyolefin foams used for foam tapes for fixing electronic devices (see, for example, patent document 1).

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2017-66403

Disclosure of Invention

Problems to be solved by the invention

In recent years, in-vehicle displays such as a Central Information Display (CID) and a Head Up Display (HUD) have been increased in size and curved, and a foam tape for fixing a panel of a module is required to have flexibility. Further, heat may be applied to the module due to the influence of sunlight or the like, and heat resistance to the fixing foam tape is also required.

As one of the simple methods for imparting heat resistance to the foam base material, it is conceivable to use a resin having a high melting point as a raw material. On the other hand, a foam using a high-melting-point resin generally becomes hard in terms of resin characteristics thereof, and as a result, the flexural modulus of the base material increases, and it is considered that a decrease in the curved surface following property (tape lifting) when used for a tape application becomes a problem.

Accordingly, an object of the present invention is to provide a polyolefin resin foam sheet having high heat resistance and excellent curved surface conformability, and an adhesive tape using the polyolefin resin foam sheet.

Means for solving the problems

The present invention has been made in view of the above-mentioned problems, and has been made to solve the problems by using a foam sheet having a specific flexural modulus of elasticity and a specific thermal shrinkage ratio.

Namely, the present invention provides the following [1] to [9 ].

[1] A polyolefin resin foam sheet having a flexural modulus of elasticity of 150kPa or less and a shrinkage percentage in the in-plane direction of 5% or less after curing at a temperature of 120 ℃ for 1 hour.

[2] The polyolefin resin foam sheet according to [1], wherein the average cell diameter of the cell diameter in the MD direction and the cell diameter in the TD direction is 400 μm or less.

[3] The polyolefin resin foam sheet according to the above [1] or [2], which is obtained by foaming a resin composition containing a resin (A) having a structural unit derived from propylene, wherein the content of the resin (A) in the resin composition is 25 to 95 parts by mass per 100 parts by mass of a resin component of the resin composition.

[4] The polyolefin resin foam sheet according to the above [3], wherein the resin (A) comprises at least 1 resin selected from the group consisting of a polypropylene resin, an ethylene-propylene random copolymer rubber and an olefin thermoplastic elastomer, the resin having a structural unit derived from propylene.

[5] The polyolefin resin foam sheet according to the above [4], wherein the resin (A) comprises the polypropylene resin and the olefin thermoplastic elastomer.

[6] The polyolefin resin foam sheet according to the above [4] or [5], wherein the polypropylene resin is a random polypropylene.

[7] The polyolefin resin foam sheet according to any one of the above [1] to [6], which has a thickness of 0.03 to 1.5 mm.

[8]According to the above [1]～[7]The polyolefin resin foam sheet according to any one of the above items, which has an apparent density of 0.05 to 0.6g/cm³。

[9] An adhesive tape comprising the polyolefin resin foam sheet according to any one of [1] to [8] and an adhesive layer provided on at least one surface of the polyolefin resin foam sheet.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a polyolefin resin foam sheet having high heat resistance and excellent curved surface conformability and an adhesive tape using the polyolefin resin foam sheet can be provided.

Detailed Description

[ polyolefin resin foam sheet ]

The polyolefin resin foam sheet of the present invention (hereinafter, may be simply referred to as "foam sheet") has a flexural modulus of elasticity of 150kPa or less and a shrinkage ratio in the surface direction after curing at 120 ℃ for 1 hour of 5% or less. This can provide a foam sheet having high heat resistance and excellent curved surface conformability. The foam sheet of the present invention is described in detail below.

(flexural modulus of elasticity)

The foam sheet of the present invention has a flexural modulus of elasticity of 150kPa or less. If the flexural modulus of elasticity of the foam sheet of the present invention is greater than 150kPa, the foam sheet may have insufficient curve following properties. The foam sheet preferably has a flexural modulus of 100kPa or less, more preferably 50kPa or less, from the viewpoint of curved surface conformability. The lower limit of the flexural modulus of the foam sheet is not particularly limited, and is, for example, 5kPa or more. The flexural modulus can be measured by the method described in the examples below.

(shrinkage in the planar direction after curing at 120 ℃ for 1 hour)

The foam sheet of the present invention has a shrinkage rate in the in-plane direction of 5% or less after curing at a temperature of 120 ℃ for 1 hour. If the shrinkage ratio of the foam sheet in the surface direction after curing at a temperature of 120 ℃ for 1 hour is more than 5%, a foam sheet having sufficient heat resistance for use in a high-temperature environment in a vehicle may not be obtained. From the viewpoint of heat resistance, the shrinkage ratio of the foam sheet in the surface direction after curing at a temperature of 120 ℃ for 1 hour is preferably 4.5% or less, more preferably 3.5% or less, and still more preferably 3% or less. The lower limit of the range of the shrinkage rate of the foam sheet in the in-plane direction after curing at a temperature of 120 ℃ for 1 hour is not particularly limited, and is, for example, 0.1%. Further, according to JIS K6767, the dimensional change at 120 ℃ of the foam sheet was measured, and the heat shrinkage (%) was calculated, and this value was defined as the shrinkage in the plane direction of the foam sheet after curing at 120 ℃ for 1 hour.

Further, from the viewpoint of having both high heat resistance and excellent curved surface following property, it is more preferable that the flexural modulus is within the above range and the shrinkage rate in the surface direction after curing at a temperature of 120 ℃ for 1 hour is within the above range.

(average cell diameter in MD and TD directions)

The foam sheet of the present invention preferably has an average cell diameter in the MD direction and TD direction of 400 μm or less. If the average cell diameter in the MD direction and TD direction is 400 μm or less, the mechanical strength of the foam sheet is improved. Thus, after the adhesive tape having the foam sheet is attached, the foam sheet can be peeled off without breaking the foam sheet (without causing interlayer breakage) when the foam sheet is peeled off for attachment. Namely, the reworkability becomes good. In the present invention, "MD" means a Machine Direction (Machine Direction) and is a Direction corresponding to the extrusion Direction of the sheet or the like. "TD" refers to a Transverse Direction (Transverse Direction) and is a Direction perpendicular to the MD and parallel to the sheet surface. From the viewpoint of reworkability, mechanical strength and curved surface conformability, the average cell diameter in the MD direction and the TD direction is more preferably 350 μm or less, and still more preferably 300 μm or less. From the viewpoint of the curved surface followability, the average cell diameter in the MD direction and the TD direction is preferably 150 μm or more, and more preferably 200 μm or more. The average cell diameter in the MD direction and the TD direction can be measured by the method described in the examples. Further, the average cell diameter in the MD direction and the TD direction can be adjusted by adjusting the gel fraction of the resin composition when producing the foam sheet.

(average bubble diameter of ZD)

The average cell diameter of the cells in the foam sheet of the present invention in the ZD direction is preferably 40 μm or more. When the average bubble diameter in the ZD direction is 40 μm or more, the curved surface followability becomes good. From the viewpoint of the following ability to a curved surface, the average bubble diameter in the ZD direction is more preferably 50 μm or more, and still more preferably 80 μm or more. From the viewpoint of reworkability, the average bubble diameter in the ZD direction is preferably 300 μm or less, more preferably 200 μm or less. Further, "ZD" means the thickness direction. The average bubble diameter of ZD can be measured according to the method described in the examples. The average cell diameter in the ZD direction of the foam sheet can be adjusted by adjusting the gel fraction of the resin composition when the foam sheet is produced.

(thickness)

The foam sheet of the present invention preferably has a thickness of 0.03 to 1.5 mm. If the thickness of the foam sheet is 0.03mm or more, the foam sheet is less likely to be heat-shrunk. Further, sufficient sealing properties can be maintained when applied to electronic devices and the like. If the thickness of the foam sheet is 1.5mm or less, the foam sheet is not excessively thick, and therefore, the foam sheet is suitable for use in electronic devices or in-vehicle electronic devices. From the above viewpoint, the thickness of the foam sheet is more preferably 0.05mm or more, still more preferably 0.1mm or more, and still more preferably 0.15mm or more, and further more preferably 1.3mm or less, still more preferably 1.1mm or less, and still more preferably 1.0mm or less.

(apparent Density)

The foam sheet of the present invention preferably has an apparent density of 0.05 to 0.6g/cm³. When the foam sheet has an apparent density of 0.05 to 0.6g/cm³The foam sheet can have improved heat resistance and can have a good balance between flexibility and mechanical strength. From the above viewpoint, the foam sheet preferably has an apparent density of 0.07 to 0.4g/cm³More preferably 0.1 to 0.3g/cm³。

(gel fraction)

The foam sheet of the present invention preferably has a gel fraction of 15 to 60 mass%. When the gel fraction of the foam sheet is 15 to 60 mass%, the average cell diameters of MD and TD of the cells of the foam sheet can be easily adjusted to a desired range. From such a viewpoint, the gel fraction of the foamed sheet is more preferably 20 to 45 mass%. The gel fraction was measured by the method described in the examples below.

(resin composition (B))

The foam sheet of the present invention is preferably obtained by foaming a resin composition (hereinafter, sometimes referred to as "resin composition (B)") containing a resin (a) having a structural unit derived from propylene (hereinafter, sometimes referred to simply as "resin (a)"). Further, the foam sheet of the present invention is more preferably a foam sheet obtained by crosslinking and foaming the resin composition (B).

The content of the resin (a) in the resin composition (B) is preferably 25 to 95 parts by mass based on 100 parts by mass of the resin component of the resin composition (B). By foaming such a resin composition (B), a foam sheet having higher heat resistance can be obtained. From such a viewpoint, the content of the resin (a) in the resin composition (B) is more preferably 50 to 90 parts by mass, still more preferably 60 to 80 parts by mass, and still more preferably 70 to 75 parts by mass with respect to 100 parts by mass of the resin component of the resin composition (B).

The resin (a) preferably contains at least 1 resin having a structural unit derived from propylene selected from the group consisting of polypropylene-based resins, ethylene-propylene random copolymer rubbers, and olefin-based thermoplastic elastomers. By foaming the resin composition (B) containing such a resin (a), a foam sheet having further improved heat resistance can be obtained. The content of at least 1 resin having a propylene-derived structural unit selected from the group consisting of a polypropylene-based resin, an ethylene-propylene random copolymer rubber, and an olefin-based thermoplastic elastomer in the resin (a) is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, and still more preferably 95 to 100% by mass, from the viewpoint of heat resistance of the foam sheet.

< Polypropylene resin >

The heat resistance of the foam sheet can be further improved by including the polypropylene resin in the resin (a). Further, by including the propylene-based resin in the resin (a), the mechanical strength of the foam can be improved, and the reworkability can be improved.

The polypropylene resin is not particularly limited, and examples thereof include copolymers of propylene and other olefins. The copolymer of propylene with another olefin may be any of a block copolymer, a random copolymer, and a random block copolymer, but is preferably a random copolymer of propylene (random polypropylene). By using the random polypropylene, the foam sheet is likely to have good following properties on curved surfaces.

In the copolymer of propylene and another olefin, examples of the other olefin to be copolymerized with propylene include α -olefins such as ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-nonene, and 1-decene, and ethylene is particularly preferable among them. That is, as the random copolymer of propylene (random polypropylene), an ethylene-propylene random copolymer is more preferable.

The content of the polypropylene resin in the resin composition (B) is preferably 20 to 70 parts by mass per 100 parts by mass of the resin component of the resin composition (B). By foaming such a resin composition (B), a foam sheet having higher heat resistance and more excellent curved surface conformability can be obtained. From such a viewpoint, the content of the polypropylene resin in the resin composition (B) is more preferably 30 to 60 parts by mass, and still more preferably 35 to 55 parts by mass, based on 100 parts by mass of the resin component of the resin composition (B).

< ethylene-propylene random copolymer rubber >

By including the ethylene-propylene random copolymer rubber in the resin (a), flexibility of the foam sheet is improved, and curved surface conformability is improved. The ethylene-propylene random copolymer rubber is an amorphous or low-crystalline rubber-like substance in which ethylene and propylene are substantially randomly copolymerized.

The ethylene-propylene random copolymer rubber may have other monomer units in addition to the ethylene unit and the propylene unit. Examples of the monomer forming the other monomer unit include conjugated dienes having 4 to 8 carbon atoms such as 1, 3-butadiene, 2-methyl-1, 3-butadiene (isoprene), 1, 3-pentadiene and 2, 3-dimethyl-1, 3-butadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, 1, 4-hexadiene, 1, 5-bicyclooctadiene and 7-methyl-1, 6-octadiene, non-conjugated dienes having 5 to 15 carbon atoms such as 5-vinyl-2-norbornene, vinyl ester compounds such as vinyl acetate, unsaturated carboxylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, and ethyl methacrylate, and unsaturated carboxylic acids such as acrylic acid and methacrylic acid. These monomers may be used alone or in combination of 2 or more. Among them, a non-conjugated diene having 5 to 15 carbon atoms is preferable, and from the viewpoint of availability, 5-ethylidene-2-norbornene, 1, 4-hexadiene, and dicyclopentadiene (DCPD) are more preferable.

The ethylene-propylene random copolymer rubber usually contains 30 to 85 mass%, preferably 40 to 80 mass%, and more preferably 45 to 75 mass% of ethylene units, 10 to 60 mass%, and preferably 15 to 50 mass% of propylene units, and 0 to 20 mass%, and preferably 1 to 10 mass% of other monomer units such as a non-conjugated diene.

The ethylene-propylene random copolymer rubber is more preferably an ethylene-propylene copolymer rubber (EPR) and an ethylene-propylene-diene copolymer rubber (EPDM), and is further preferably an EPDM. Further, the EPDM includes ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber and ethylene-propylene-dicyclopentadiene copolymer rubber, and among them, ethylene-propylene-dicyclopentadiene copolymer rubber is preferable.

These ethylene-propylene random copolymer rubbers may be used alone or in combination of 2 or more.

The content of the ethylene-propylene random copolymer rubber in the resin component of the resin composition (B) is preferably 5 to 40 parts by mass, more preferably 10 to 30 parts by mass, and still more preferably 15 to 25 parts by mass, per 100 parts by mass of the resin component.

In this way, the foam sheet can have good flexibility by setting the content of the ethylene-propylene random copolymer rubber in the resin component of the resin composition (B) to 5 to 40 parts by mass with respect to 100 parts by mass of the resin component.

< olefinic thermoplastic elastomer (TPO) >)

Olefin-based thermoplastic elastomers (TPOs) are generally thermoplastic elastomers having a polyolefin-based resin such as a polyethylene-based resin or a polypropylene-based resin as a hard segment and a polyolefin-based rubber such as EPR or EPDM as a soft segment. TPO can be used in any of blend type, dynamic crosslinking type, and polymerization type.

In the TPO used for the foam sheet of the present invention, the polyolefin compound of at least one of the polyolefin resin and the polyolefin rubber has a structural unit derived from propylene. When the resin (a) contains such TPO, the heat resistance and the curved surface conformability of the foam sheet can be improved in a good balance. The TPO used in the foam sheet of the present invention is more preferably one in which both the polyolefin resin and the polyolefin rubber have a propylene-derived structural unit. The polyolefin resin is more preferably a polypropylene resin.

Examples of commercially available TPOs used in the foam sheet of the present invention include those manufactured by LyondellBASEll corporation under the product name "Softell CA 02A".

The content of TPO in the resin component of the resin composition (B) is preferably 1 to 35 parts by mass, more preferably 2 to 25 parts by mass, and still more preferably 3 to 20 parts by mass, per 100 parts by mass of the resin component.

In this way, the foam sheet can have good heat resistance and good curved surface conformability by setting the content of TPO in the resin component of the resin composition (B) to 1 to 35 parts by mass with respect to 100 parts by mass of the resin component.

When the resin (A) contains a polypropylene-based resin, the foam sheet has higher heat resistance and improved reworkability. Further, if the resin (a) further contains an olefin-based thermoplastic elastomer (TPO), the curved surface followability of the foam sheet can be further improved while maintaining high heat resistance and good reworkability by the polypropylene-based resin. From such a viewpoint, the resin (a) preferably contains a polypropylene-based resin and an olefin-based thermoplastic elastomer (TPO). In addition, the resin (a) further improves the following property to a curved surface by containing an ethylene-propylene random copolymer rubber in addition to the polypropylene resin and the olefin thermoplastic elastomer (TPO). From such a viewpoint, the resin (a) more preferably contains a polypropylene-based resin, an olefin-based thermoplastic elastomer (TPO), and an ethylene-propylene random copolymer rubber.

< polyethylene resin >

The resin composition (B) may further contain a polyethylene resin. This improves the compatibility of the resin component in the resin composition (B). Examples of the polyethylene resin include a low-density polyethylene resin, a medium-density polyethylene resin, a high-density polyethylene resin, and a linear low-density polyethylene resin, but among them, a linear low-density polyethylene resin (LLDPE) is preferable.

The linear low-density polyethylene resin has a density of 0.910g/cm³Above and less than 0.950g/cm³The polyethylene (B) preferably has a density of 0.910 to 0.930g/cm³The polyethylene of (1). By containing a linear low-density polyethylene resin having a low density in the foam, the foam is likely to have good processability when the resin composition is processed into a foam, moldability when the foam is molded into a molded article, and the like. The density of the resin was measured according to JIS K7112.

The linear low-density polyethylene is generally a copolymer of ethylene and a small amount of α -olefin, the copolymer having ethylene as a main component (80% by mass or more, preferably 90% by mass or more, and more preferably 95% by mass or more of the total monomers). The α -olefin includes an α -olefin having 3 to 12 carbon atoms, preferably 4 to 10 carbon atoms, and specifically includes 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, and the like. In addition, in the copolymer, these alpha-olefins can be used alone or in combination of 2 or more.

Further, the polyethylene resin may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

The content of the polyethylene resin in the resin component of the resin composition (B) is preferably 5 to 75 parts by mass, more preferably 5 to 45 parts by mass, still more preferably 15 to 35 parts by mass, and particularly preferably 20 to 30 parts by mass, based on 100 parts by mass of the resin component.

In this way, the content of the polyethylene resin in the resin component of the resin composition (B) is 5 to 75 parts by mass with respect to 100 parts by mass of the resin component, and the compatibility of the resin component in the resin composition (B) is further improved.

The resin composition (B) more preferably contains a polypropylene-based resin, an ethylene-propylene random copolymer rubber, an olefin-based thermoplastic elastomer, and a polyethylene-based resin from the viewpoint of further improving the heat resistance of the foam sheet and further improving the curved surface conformability by improving the compatibility of the resin components of the resin composition (B).

< other resin component >

The resin composition (B) may contain resin components other than the polypropylene-based resin, the ethylene-propylene random copolymer rubber, the olefin-based thermoplastic elastomer, and the polyethylene-based resin, as long as the object of the present invention is not impaired. Examples of such a resin component include an ethylene-vinyl acetate copolymer, an ethylene-acrylic acid copolymer, an ethylene- (meth) alkyl acrylate copolymer, and a modified copolymer obtained by copolymerizing these with maleic anhydride.

The total content of the polypropylene-based resin, the ethylene-propylene random copolymer rubber, the olefin-based thermoplastic elastomer, and the polyethylene-based resin in the resin composition (B) is preferably 80 to 99% by mass, and more preferably 83 to 98% by mass, from the viewpoint of improving the heat resistance and mechanical strength of the foam sheet and ensuring flexibility and moldability.

< additive >

The resin composition (B) usually contains a blowing agent as an additive in addition to the olefin-based resin. In addition, the resin composition (B) may further contain a decomposition temperature adjusting agent. Further, the resin composition (B) preferably contains one or both of a crosslinking assistant and an antioxidant.

Foaming agent

Examples of the method for foaming the resin composition (B) include a chemical foaming method and a physical foaming method. The chemical foaming method is a method of forming cells by using gas generated by thermal decomposition of a compound added to the resin composition (B), and the physical foaming method is a method of forming cells by volatilizing a foaming agent after impregnating the resin composition (B) with a low boiling point liquid (foaming agent). The foaming method is not particularly limited, but a chemical foaming method is preferable from the viewpoint of obtaining a uniform independent foam sheet.

As the foaming agent, a thermal decomposition type foaming agent is used, and for example, an organic or inorganic chemical foaming agent having a decomposition temperature of about 160 to 270 ℃ can be used.

Examples of the organic foaming agent include azodicarbonamide, metal salts of azodicarboxylic acid (e.g., barium azodicarboxylate), azo compounds such as azobisisobutyronitrile, nitroso compounds such as N, N '-dinitrosopentamethylenetetramine, hydrazine derivatives such as biurea, 4' -oxybis (benzenesulfonylhydrazide) and toluenesulfonylhydrazide, and semicarbazide compounds such as toluenesulfonylsemicarbazide.

Examples of the inorganic foaming agent include ammonium salt, sodium carbonate, ammonium hydrogen carbonate, sodium hydrogen carbonate, ammonium nitrite, sodium borohydride, monosodium citrate anhydride, and the like.

Among them, from the viewpoint of obtaining fine bubbles and from the viewpoint of economy and safety, azo compounds and nitroso compounds are preferable, azodicarbonamide, azobisisobutyronitrile, N' -dinitrosopentamethylenetetramine are more preferable, and azodicarbonamide is particularly preferable.

The blowing agent may be used singly or in combination of 2 or more.

The amount of the thermal decomposition type foaming agent added is preferably 1 to 25 parts by mass, more preferably 1.5 to 15 parts by mass, and even more preferably 2 to 10 parts by mass, per 100 parts by mass of the resin component, from the viewpoint of suitably foaming the foam sheet without breaking the cells.

Decomposition temperature regulator

Examples of the decomposition temperature regulator include basic magnesium salts, zinc oxide, zinc stearate, urea, and the like. These decomposition temperature regulators can be used alone in 1, or in combination of more than 2. Among these decomposition temperature regulators, basic magnesium salts are preferable. Further, the basic magnesium preferable as the decomposition temperature regulator is at least 1 magnesium compound selected from magnesium oxide and magnesium hydroxide. The resin composition (B) may contain either magnesium oxide or magnesium hydroxide, or both. By blending a decomposition temperature foaming agent in the resin composition (B), the decomposition temperature of the thermal decomposition type foaming agent can be adjusted, and thereby the cell diameter of the foam sheet can be adjusted.

When the foaming agent, particularly azodicarbonamide, is decomposed by heating, a part thereof turns into a sublimate and fogging occurs. However, the resin composition (B) contains basic magnesium to prevent fogging due to such sublimates. Therefore, in the present invention, when azodicarbonamide is used as the blowing agent, the resin composition (B) preferably contains basic magnesium.

The content of the decomposition temperature modifier in the resin composition (B) is preferably 0.03 to 3.0 parts by mass, more preferably 0.04 to 2.0 parts by mass, and still more preferably 0.05 to 1.5 parts by mass, per 100 parts by mass of the resin component.

Crosslinking aid

As the crosslinking assistant, a polyfunctional monomer may be used. Examples thereof include 3-functional (meth) acrylate compounds such as trimethylolpropane trimethacrylate and trimethylolpropane triacrylate, triallyl trimellitate, triallyl 1,2, 4-benzenetricarboxylate, triallyl isocyanurate, and other compounds having 3 functional groups in 1 molecule, 1, 6-hexanediol dimethacrylate, 1, 9-nonanediol dimethacrylate, 1, 10-decanediol dimethacrylate, 2-functional (meth) acrylate compounds such as neopentyl glycol dimethacrylate, compounds having 2 functional groups in 1 molecule such as divinylbenzene, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, ethylvinylbenzene, lauryl methacrylate, stearyl methacrylate, and the like. Among them, a 3-functional (meth) acrylate compound is more preferable.

The crosslinking assistant may be used singly or in combination of 2 or more.

By adding the crosslinking assistant to the resin composition (B), the resin composition (B) can be crosslinked with a small ionizing radiation dose. Therefore, the resin molecules can be prevented from being cut or deteriorated due to the irradiation of the ionizing radiation.

In foaming the resin composition (B), the content of the crosslinking assistant is preferably 0.2 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the resin component, from the viewpoint of easiness of adjustment and control of the gel fraction.

Antioxidant agent

Examples of the antioxidant include a phenol-based antioxidant, a sulfur-based antioxidant, a phosphorus-based antioxidant, and an amine-based antioxidant. Among them, a phenol-based antioxidant and a sulfur-based antioxidant are preferable, and a phenol-based antioxidant and a sulfur-based antioxidant are more preferably used in combination.

Examples of the phenolic antioxidant include 2, 6-di-tert-butyl-p-cresol, n-octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, and tetrakis [ methylene-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] methane.

Examples of the sulfur-based antioxidant include dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, and pentaerythrityl tetrakis (3-laurylthiopropionate).

These antioxidants may be used singly or in combination of 2 or more.

The content of the antioxidant is preferably 0.1 to 10 parts by mass, and more preferably 0.2 to 5 parts by mass, per 100 parts by mass of the resin component.

The resin composition (B) may contain additives other than those described above, such as flame retardants, metal damage preventives, antistatic agents, stabilizers, fillers, and pigments, as required.

The foam sheet of the present invention has high heat resistance and excellent curved surface conformability, and is therefore suitable for use in electronic devices, particularly in-vehicle electronic devices. The display device is particularly suitable for use in vehicle-mounted image display devices such as a Center Information Display (CID) and a head-up display (HUD).

< method for producing foam sheet >

The foam sheet can be produced, for example, by melt-kneading the resin composition (B) to form a desired shape, and then irradiating the resin composition (B) with ionizing radiation to heat and foam the resin composition (B).

Specifically, the production method is more preferably provided with the following steps 1 to 3.

Step 1: a step of obtaining a sheet-like resin composition (B) by melt-kneading the components constituting the resin composition (B)

And a step 2: a step of irradiating the resin composition (B) obtained in the step 1 with ionizing radiation to crosslink the resin composition

Step 3: a step of heating the resin composition (B) crosslinked in the step 2 to a temperature not lower than the decomposition temperature of the thermal decomposition type foaming agent to foam the composition, thereby obtaining a foam sheet

In step 1, the respective components constituting the resin composition (B) are supplied to a kneading apparatus, melt-kneaded at a temperature lower than the decomposition temperature of the thermal decomposition type foaming agent, and then the melt-kneaded resin composition (B) is preferably molded into a sheet by the kneading apparatus used for melt-kneading.

Examples of the kneading apparatus used herein include general-purpose kneading apparatuses such as an injection molding machine, an extruder (a single-screw extruder, a twin-screw extruder, etc.), a banbury mixer, and a roll, but the apparatus is preferably an injection molding machine or an extruder, and if an injection molding machine is used, the apparatus can be produced with good productivity.

The resin temperature inside the injection molding machine or the extruder is preferably 120 to 220 ℃, more preferably 140 to 200 ℃, and further preferably 150 to 195 ℃.

In step 2, the resin composition (B) molded into a sheet shape is irradiated with ionizing radiation.

Examples of the ionizing radiation include electron beams, α -rays, β -rays, γ -rays, and X-rays. Among them, from the viewpoint of uniform productivity and irradiation, electron beams are preferable.

The ionizing radiation may be irradiated to only one surface of the resin composition (B) molded into a sheet form, or may be irradiated to both surfaces.

The acceleration voltage of the ionizing radiation is related to the thickness of the foamable resin composition to be irradiated, and is, for example, preferably 400 to 1200kV, more preferably 500 to 1100kV, and still more preferably 600 to 1000kV when the thickness is 0.05 to 3 mm.

The dose of ionizing radiation is not particularly limited as long as the desired gel fraction can be obtained without surface roughness or cracks in consideration of the thickness of the foamable resin composition to be irradiated, and is preferably 0.1 to 10Mrad, more preferably 0.2 to 5Mrad, and still more preferably 0.3 to 3 Mrad.

In step 3, the resin composition (B) is crosslinked by irradiation with ionizing radiation as described above, and then the resin composition (B) is heated to a temperature equal to or higher than the decomposition temperature of the foaming agent to be foamed, thereby obtaining a foam sheet. After the resin composition (B) is foamed, or while the resin composition (B) is foamed, the resin composition (B) may be stretched in either or both of the MD direction and the CD direction.

The temperature for heating and foaming the resin composition (B) is usually 140 to 300 ℃, preferably 150 to 280 ℃, and more preferably 160 to 260 ℃, although it is related to the decomposition temperature of the thermal decomposition type foaming agent used as the foaming agent.

The foam sheet of the present invention is preferably of an independent cell structure, but may be of an independent cell structure containing open cells.

[ adhesive tape ]

The adhesive tape of the present invention is an adhesive tape using the foam sheet as a base material, and specifically includes a foam sheet and an adhesive layer provided on at least one surface of the foam sheet.

The thickness of the adhesive layer constituting the adhesive tape is preferably 5 to 200 μm, more preferably 7 to 150 μm, and still more preferably 10 to 100 μm.

The adhesive tape of the present invention is preferably provided with an adhesive layer on both surfaces of the foam sheet. That is, the adhesive tape of the present invention is preferably a double-sided tape.

Further, the adhesive tape of the present invention can seal even a gap having a curved surface, and therefore can be suitably used as a sealing material for electronic equipment used for more reliably preventing dust, moisture, and the like from entering from the outside to the inside of the electronic equipment having a curved surface, and particularly can be suitably used as a sealing material for in-vehicle electronic equipment.

The adhesive constituting the adhesive layer is not particularly limited, and examples thereof include an acrylic adhesive, a urethane adhesive, a rubber adhesive, and a silicone adhesive.

Examples of the method of applying the adhesive to the foam sheet and laminating the adhesive layer on the foam sheet include a method of transferring the adhesive applied to a release paper to the foam sheet, a method of applying the adhesive to at least one surface of the foam sheet using a coating machine such as a coater, a method of spraying the adhesive to at least one surface of the foam sheet using a sprayer, a method of applying the adhesive to one surface of the foam sheet using a brush, and a method of attaching a double-sided tape having adhesive layers on both surfaces to the foam sheet.

The adhesive tape of the present invention uses a foam sheet having high heat resistance and excellent curved surface conformability as a base material, and is therefore suitable for use in electronic devices, particularly in-vehicle electronic devices. The display device is particularly suitable for use in an in-vehicle image display device such as a center information display (CID, Head Up Display (HUD)).

Examples

The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

The methods of measuring the physical properties and the methods of evaluating the foam sheet are as follows.

(1) Fraction of gel

A test piece of about 100mg was sampled from the foam sheet, and the mass A (mg) of the test piece was precisely measured. Next, the test piece was immersed in xylene at 120 ℃ for 30cm³After leaving for 24 hours, the insoluble matter on the gauze was collected by filtration through a 200-mesh wire gauze, dried under vacuum, and the mass B (mg) of the insoluble matter was precisely measured. From the obtained values, gel fraction (% by mass) was calculated by the following equation.

Gel fraction (mass%) (100 × (B/a)

(2) Density of foam sheet

The density (apparent density) of the foam sheet was measured in accordance with JIS K7222.

(3) Thickness of foam sheet

The thickness of the foam sheet was measured using a direct-reading thickness meter.

(4) Heating shrinkage (120 ℃ C.. times.1 hr)

The dimensional change at 120 ℃ of the foam sheet was measured according to JIS K6767, and the heat shrinkage (%) was calculated, and this value was taken as the shrinkage in the planar direction of the foam sheet after curing at 120 ℃ for 1 hour.

(5) Modulus of elasticity in bending

The foam sheet was cut into a width of 25mm and a length of 30mm, the sheets were stacked so that the thickness became 30mm, and the flexural modulus of elasticity was measured by using テンシロン (product name: RTC-1310A manufactured by ORIENTEC) in accordance with another test method using JIS 7171, 7221-2 as a reference.

As a calculation method, the elongation mm measured by the above method is plotted on the horizontal axis and the load N is plotted on the vertical axis, and the value of the slope at which the slope of the plot in the range of 0.5mm to 5mm of the elongation becomes maximum is defined as the flexural modulus.

(6) Average bubble diameter

The foam sheet was cut into a 50mm square, immersed in liquid nitrogen for 1 minute, then cut along each of MD and TD, and a 200-fold magnified photograph was taken with a digital microscope (product name: VHX-900, manufactured by Kokai キーエンス). In the foam sheet of the photographed image, the cell diameters of MD or TD and ZD were measured for all cells present in a cut surface of 2mm parts in length in each of MD and TD, and this operation was repeated 5 times. Further, the average value of the bubble diameters of MD and TD (average bubble diameter) and the average value of the bubble diameters of ZD (average bubble diameter) were calculated.

(7) Following property of curved surface

The foam sheet was allowed to stand at 90 ℃ for 24 hours while having an adhesive layer and being stuck to an acrylic plate having R ═ 0.095. Then, the adhered portion was confirmed, and the curved surface followability was evaluated by the presence or absence of tape floating and wrinkle generation. The evaluation was "o" when there was no tape float and no wrinkle, and "x" when at least one of the wrinkles occurred.

(8) Reworkability

The foam sheet was allowed to have an adhesive layer on both sides, and acrylic plates were attached to both sides and left to stand at 23 ℃ for 24 hours. Then, the bonded acrylic plate was peeled off, and the case where the adhesive layer interface was broken was regarded as having reworkability and evaluated as "o", and the case where the adhesive layer interface was not broken was regarded as not having reworkability and evaluated as "x".

(preparation of foam sheets of examples 1 to 8 and comparative examples 1 to 2)

< example 1 >

40 parts by mass of random PP, 20 parts by mass of EPDM, 15 parts by mass of TPO, 25 parts by mass of LLDPE, 3 parts by mass of a thermal decomposition type foaming agent, 1 part by mass of a decomposition temperature regulator, 0.5 part by mass of an antioxidant, and 3 parts by mass of a crosslinking aid were fed into a single-screw extruder. Further, the above raw materials were melt kneaded at a resin temperature of 180 ℃ and extruded to obtain a sheet-like resin composition having a thickness of 0.36 mm. The sheet-like resin composition was irradiated with electron beams on both sides thereof to crosslink the resin composition so that the gel fraction was 30 mass%. Then, the crosslinked resin composition was heated at 250 ℃ for 5 minutes by an air heater while being stretched in the MD direction and the TD direction, and foamed by the heating, whereby an apparent density of 0.2g/cm was obtained ³The foam sheet of example 1 having a thickness of 0.3 mm.

< example 2 >

An apparent density of 0.2g/cm was obtained by the same production method as that for the foam sheet of example 1, except that the thickness of the sheet-like resin composition was adjusted to 0.26mm³The foam sheet of example 2 having a thickness of 0.2 mm.

< example 3 >

An apparent density of 0.075g/cm was obtained in the same manner as in the production method of the foam sheet of example 1, except that the mixing amount of the thermal decomposition type foaming agent was changed from 3 parts by mass to 6 parts by mass³Thickness of 1.0mmThe foam sheet of example 3.

< example 4 >

An apparent density of 0.3g/cm was obtained by the same production method as that of the foam sheet of example 1, except that the mixing amount of the thermal decomposition type foaming agent was changed from 3 parts by mass to 2 parts by mass³The foam sheet of example 4 having a thickness of 0.35 mm.

< example 5 >

The compounding amount of the random PP was changed from 40 parts by mass to 50 parts by mass, the compounding amount of TPO was changed from 15 parts by mass to 5 parts by mass, and the compounding amount of the thermal decomposition type foaming agent was changed from 3 parts by mass to 6 parts by mass. Except for this, in the same manner as in the foam sheet of example 1, an apparent density of 0.075g/cm was obtained ³The foam sheet of example 5 having a thickness of 1.0 mm.

< example 6 >

The mixing amount of the thermal decomposition type foaming agent was changed from 3 parts by mass to 2.5 parts by mass, and the irradiation dose of the electron beam was changed to change the gel fraction of the resin composition from 30% by mass to 20% by mass. Except for this, the same production method as that for the foam sheet of example 1 was used, whereby an apparent density of 0.2g/cm was obtained³The foam sheet of example 6 having a thickness of 0.3 mm.

< example 7 >

The mixing amount of the thermal decomposition type foaming agent was changed from 3 parts by mass to 2.5 parts by mass, and the irradiation dose of the electron beam was changed to change the gel fraction of the resin composition from 30% by mass to 15% by mass. Except for this, the same production method as that for the foam sheet of example 1 was used, whereby an apparent density of 0.2g/cm was obtained³The foam sheet of example 7 having a thickness of 0.3 mm.

< example 8 >

The mixing amount of the thermal decomposition type foaming agent was changed from 3 parts by mass to 5.5 parts by mass, and the irradiation dose of the electron beam was changed to change the gel fraction of the resin composition from 30% by mass to 20% by mass. Except for this, in the same manner as in the foam sheet of example 1, an apparent density of 0.075g/cm was obtained ³Thickness of 1.0mmThe foam sheet of example 8.

< comparative example 1 >

The amount of the random PP was changed from 40 parts by mass to 55 parts by mass, and the amount of the thermal decomposition type foaming agent was changed from 3 parts by mass to 5.5 parts by mass without adding TPO. Except for this, in the same manner as in the foam sheet of example 1, an apparent density of 0.075g/cm was obtained³The foam sheet of comparative example 1 having a thickness of 1.0 mm.

< comparative example 2 >

Random PP, EPDM and TPO were not compounded, the amount of LLDPE was changed from 25 parts by mass to 100 parts by mass, and a crosslinking aid was not compounded. Except for this, the same production method as that for the foam sheet of example 1 was used, whereby an apparent density of 0.2g/cm was obtained³The foam sheet of comparative example 1 having a thickness of 0.3 mm.

The physical properties and evaluation results of the foam sheet are shown in tables 1 to 3.

[ Table 1]

TABLE 1

[ Table 2]

TABLE 2

[ Table 3]

TABLE 3

The details of the resin components and additives shown in tables 1 to 3 are as follows.

Random PP: ethylene-propylene random copolymer, manufactured by japan ポリプ kokai corporation, product name: ノ^ミテツク EG7F, MFR: 1.3g/10 min, ethylene content: 3% by mass

EPDM: ethylene-propylene-diene copolymer, manufactured by sumitomo chemical corporation, trade name: industrial スプレン 301, Mooney viscosity (ML) ₁₊₄100 ℃), 55, ethylene content: 62 mass%, propylene content: 35 mass%, dicyclopentadiene (DCPD) content: 3% by mass

TPO: olefinic thermoplastic elastomer, available from LyondellBASEll, trade name: softell ca 02A, MFR: 0.6g/10 minutes of the reaction solution,

LLDPE: linear low-density polyethylene manufactured by ダウケミカル, trade name: 2036P, MFR: 2.5g/10 min

Thermal decomposition type foaming agent: azodicarbonamide

Decomposition temperature regulator: magnesium oxide, magnesium hydroxide

Antioxidant: 2, 6-di-tert-butyl-p-cresol dilaurylthiodipropionate

Crosslinking assistant agent: trimethylolpropane trimethacrylate

By comparing examples 1 to 8 with comparative examples 1 to 2, it is understood that a foam sheet having high heat resistance and excellent curved surface conformability can be obtained by setting the flexural modulus of elasticity of the foam sheet to 150kPa or less and setting the shrinkage rate in the planar direction after curing at a temperature of 120 ℃ for 1 hour to 5% or less. Further, it is understood that by comparing examples 1 to 6 with examples 7 to 8, the foam sheet having an average cell diameter of MD and TD of 400 μm or less can be obtained, and thus a foam sheet having further excellent reworkability can be obtained.