Fiber Resin Composite

Abstract

To provide a fiber resin composite sheet which is excellent in water repellency and tack suppression effect, hardly produces wrinkles, folding marks and dents when folded, and has excellent resistance to repeated folding. The fiber-resin composite is made by impregnating one or more sheet-shaped short fiber aggregates with a resin composition, and the total basis weight of the short fiber aggregates is 5 g / m 2 More than 80g / m 2 or less, the average fiber length of the short fibers is 2 mm or more and 30 mm or less, the resin composition contains a 4-methyl-1-pentene copolymer (A) in which the content of structural units (P) derived from 4-methyl-1-pentene and the content of structural units (AQ) derived from a monomer selected from the group consisting of ethylene and linear or branched α-olefins having 3 to 20 carbon atoms are within a specific range, and the short fibers are exposed on at least one outer surface of the fiber composite.

Description

[Technical Field]

[0001] The present invention relates to a fiber resin composite in which one or more sheet-like short fiber aggregates are impregnated with a resin composition, a method for producing the same, and daily necessities, refrigerator containers, toys, etc. containing the same. [Background technology]

[0002] Washi is a type of paper unique to Japan that has been produced since ancient times and is still widely used in everyday life to this day. It is primarily made from a variety of raw materials, including hemp, kozo (paper mulberry), mitsumata (rice bracken), gampi (gampi), mulberry, and bamboo. Because the long fibers are intertwined, it is thinner and less likely to tear than Western paper, which has shorter fibers, and has a supple feel. Furthermore, the material has a large surface area and is highly capable of absorbing moisture from the air, so it is also used to regulate humidity. However, in environments where it is constantly in contact with moisture, the bonds between the fibers weaken as water seeps in, causing the paper to tear.

[0003] Due to recent advances in packaging materials and changes in consumer behavior, there is an increasing demand for design and luxury in traditional packaging materials, storage containers, and industrial sheets. The following Patent Document 1 discloses a retort pouch made of a packaging material in which Japanese paper is laminated on the outermost surface. However, due to problems with heat resistance and water resistance, a nonwoven fabric made of synthetic resin has been proposed as an alternative to the Japanese paper. On the other hand, as described in Patent Documents 2 and 3 below, 4-methyl-1-pentene copolymers are known to have superior stress relaxation properties, water repellency, mold releasability, etc. compared to thermoplastic elastomers or rubbers, and to exhibit a good fit and relaxation properties when formed into a composite with a film, fabric, etc. Furthermore, Patent Document 4 below discloses a cooler container that can stand on its own during storage and use, taking advantage of the property that its hardness changes depending on the temperature. However, no fiber-branch composite has yet been provided that can achieve the texture and appearance of Japanese paper, as well as stress relaxation properties and self-supporting properties when kept cold, and further improvement is needed. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2007-008477 [Patent Document 2] International Publication No. 2018 / 143411 [Patent Document 3] International Publication No. 2017 / 164364 [Patent Document 4] Japanese Patent Application Publication No. 2019-58636 Summary of the Invention [Problem to be solved by the invention]

[0005] The packaging bag described in Patent Document 1 has problems such as the heat resistance of the surface printing ink and the water resistance of Japanese paper, and therefore a laminate of synthetic resin and nonwoven fabric is being considered as an alternative material. Furthermore, the 4-methyl-1-pentene copolymer used in Patent Documents 2 to 4 has excellent stress relaxation properties, temperature responsiveness, and stretchability, but is prone to stickiness due to surface tackiness and deformation due to stretching during use. Further improvement was needed to achieve a texture and appearance similar to Japanese paper, stress relaxation properties, and self-standing ability when kept cold while maintaining the shape. In view of the state of the prior art, the problem that the present invention aims to solve is to provide a sheet-like fiber-resin composite that has excellent water repellency and tack suppression effects, is less likely to develop wrinkles, creases, or dents when folded, and does not break, fray, or tear even when repeatedly folded, as well as a method for producing the same, and a cooler container or the like that includes the same. [Means for solving the problem]

[0006] That is, the present invention is as follows. [1] A fiber-resin composite in which one or more sheet-shaped short fiber aggregates are impregnated with a resin composition, The total basis weight of the short fiber aggregate is 5 g / m 2More than 80g / m 2 and the average fiber length of the short fibers constituting the short fiber aggregate is 2 mm or more and 30 mm or less, and The resin composition satisfies the following requirement (Aa): (Aa) the content of structural units (P) derived from 4-methyl-1-pentene is 65 mol% or more and less than 90 mol%, and the content of structural units (AQ) derived from monomers selected from the group consisting of ethylene and linear or branched α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is more than 10 mol% and 35 mol% or less; The 4-methyl-1-pentene copolymer (A) satisfies the above formula (1), and The short fibers are exposed on at least one outer surface of the fiber composite. A fiber resin composite characterized by: [2] The fiber resin composite according to [1], wherein the structural unit (AQ) comprises a structural unit derived from a monomer selected from the group consisting of ethylene and an α-olefin having 3 to 4 carbon atoms. [3] The 4-methyl-1-pentene copolymer (A) further satisfies the following requirement (Ab): (Ab) No melting point (Tm) is observed by differential scanning calorimetry (DSC). The fiber resin composite according to [1] or [2] above, which satisfies the above. [4] The 4-methyl-1-pentene copolymer further satisfies the following requirement (Ac): (Ac) The peak temperature of the loss tangent tanδ obtained by dynamic viscoelasticity measurement in the temperature range of -40 to 150°C at a frequency of 10 rad / s (1.6 Hz) is in the range of 15°C to 45°C, and the following requirements are met: (Ad) (Ad) The peak value of the loss tangent tanδ obtained by dynamic viscoelasticity measurement in the temperature range of -40 to 150°C and at a frequency of 10 rad / s (1.6 Hz) is in the range of 1.0 to 5.0. The fiber resin composite according to any one of the above [1] to [3], which satisfies the above. [5] The total basis weight of the short fiber aggregate is 5 g / m 2 More than 50g / m 2The fiber resin composite according to any one of the above [1] to [4], which is as follows: [6] The fiber resin composite according to any one of [1] to [5], wherein the average fiber length of the short fibers constituting the short fiber aggregate is 3 mm or more and 15 mm or less. [7] The fiber resin composite according to any one of [1] to [6], wherein the short fiber aggregate is a nonwoven fabric or a paper. [8] The fiber resin composite according to [7], wherein the short fiber aggregate is Japanese paper. [9] The weight of the fiber-resin composite is 100 g / m 2 More than 250g / m 2 The fiber resin composite according to any one of the above [1] to [8], which is:

[10] The fiber resin composite according to any one of [1] to [9], wherein the fiber resin composite has a thickness of 40 μm or more and 300 μm or less.

[11] The fiber resin composite according to any one of [1] to

[10] above, wherein the fiber resin composite has a tensile elongation at break of 5% or less.

[12] A daily necessities comprising the fiber resin composite according to any one of [1] to

[11] .

[13] A cold storage container comprising the fiber resin composite according to any one of [1] to

[11] .

[14] A toy comprising the fiber resin composite according to any one of [1] to

[11] .

[15] the following steps: Total basis weight: 5g / m 2 More than 80g / m 2 preparing one or more sheet-like short fiber aggregates having an average fiber length of 2 mm or more and 30 mm or less; The following requirements (Aa): (Aa) the content of structural units (P) derived from 4-methyl-1-pentene is 65 mol% or more and less than 90 mol%, and the content of structural units (AQ) derived from monomers selected from the group consisting of ethylene and linear or branched α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is more than 10 mol% and 35 mol% or less; preparing one or more sheet-shaped resin compositions containing a 4-methyl-1-pentene copolymer (A) that satisfies the above formula: a step of stacking the sheet-like short fiber aggregate and one sheet-like resin composition when the sheet-like short fiber aggregate is single, or sandwiching the single sheet-like resin composition between the plurality of sheet-like short fiber aggregates when the sheet-like short fiber aggregate is multiple, and hot pressing the resulting mixture; The method for producing a fiber resin composite according to any one of the above [1] to

[11] , comprising: [Effects of the Invention]

[0007] The fiber resin composite of the present invention not only has excellent water repellency and tack suppression effects, but also is less likely to develop wrinkles, creases, or dents when folded, and does not break, fray, or tear even when repeatedly folded. DETAILED DESCRIPTION OF THE INVENTION

[0008] The following description of the components may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In this disclosure, combinations of preferred embodiments are more preferred embodiments. In the present disclosure, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In the numerical ranges described in stages in the present disclosure, the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in the numerical ranges described in the present disclosure, the upper or lower limit value described in a certain numerical range may be replaced with a value shown in the examples. In the present disclosure, when a plurality of substances corresponding to each component are present in the composition, the amount of each component in the composition means the total amount of the plurality of substances present in the composition, unless otherwise specified. In the present disclosure, "contains mainly" means that the target substance is contained in the largest amount relative to the whole. For example, this means that the content of the target substance is 50% by mass or more relative to the whole. In this disclosure, "mass%" and "wt%" are synonymous, and "parts by mass" and "parts by weight" are synonymous. In this disclosure, "%" indicating the amount of a component is based on mass unless otherwise specified.

[0009] One embodiment of the present invention is a fiber resin composite in which one or more sheet-like short fiber aggregates are impregnated with a resin composition, The total basis weight of the short fiber aggregate is 5 g / m 2 More than 80g / m 2 and the average fiber length of the short fibers constituting the short fiber aggregate is 2 mm or more and 30 mm or less, and The resin composition satisfies the following requirement (Aa): (Aa) the content of structural units (P) derived from 4-methyl-1-pentene is 65 mol% or more and less than 90 mol%, and the content of structural units (AQ) derived from monomers selected from the group consisting of ethylene and linear or branched α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is more than 10 mol% and 35 mol% or less; The 4-methyl-1-pentene copolymer (A) satisfies the above formula (1), and The short fibers are exposed on at least one outer surface of the fiber composite. The fiber-resin composite is characterized by the above.

[0010] When a resin composition containing 4-methyl-1-pentene copolymer covers the entire outer surface of at least one of the fiber-resin composites, leaving the short fibers unexposed, the composite exhibits water repellency. However, when the composite is folded 180° and stacked, the resin compositions stick to each other, resulting in poor tack resistance. On the other hand, if the basis weight of the short fiber aggregate is too high and the average fiber length of the short fibers is too short, flexibility (the ability to resist wrinkles, creases, and dents when folded, and to resist breakage, fraying, and tearing after repeated folding) is poor. Therefore, to balance tack resistance and flexibility, it is necessary to impregnate a short fiber aggregate (e.g., Japanese paper) with specific parameters with a specific resin composition under optimal conditions. The term "the short fibers are exposed on at least one outer surface of the fiber composite" does not mean that the resin composition covers the entirety of at least one outer surface of the fiber-resin composite, but means that the resin composition is ensured to be appropriately distributed unevenly on at least one outer surface of the fiber-resin composite in order to balance tack suppression and flexibility. In the examples described later, "at least one outer surface of the fiber-resin composite" is exemplified as "short fiber aggregate interior (Y)," but this embodiment also includes an embodiment in which the short fibers are exposed on at least both outer surfaces of the fiber-resin composite.

[0011] [Fiber-resin composite] The fiber-resin composite of this embodiment is a sheet-like short fiber assembly impregnated with a resin composition containing a 4-methyl-1-pentene copolymer (A). Here, the 4-methyl-1-pentene copolymer (A) has a content of structural units (P) derived from 4-methyl-1-pentene of 65 mol% or more and less than 90 mol%, and a content of structural units (AQ) derived from ethylene and linear or branched α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) of more than 10 mol% and not more than 35 mol%. The fiber-resin composite contains a resin composition containing the above-mentioned 4-methyl-1-pentene copolymer (A), and the basis weight of the short fiber aggregate is 5 g / m 2 More than 80g / m 2When the average fiber length of the short fibers constituting the short fiber aggregate is 2 mm or more and 30 mm or less, the tack suppression and flexibility of the fiber-resin composite are both improved. That is, even when the fiber-resin composite is bent under load, cracks, wrinkles, bending marks, and dents on the exterior tend to disappear over time.

[0012] The fiber-resin composite has a water droplet contact angle immediately after application measured in an environment of 23°C and 50% humidity of 65° to 150°, preferably 68° to 120°, more preferably 70° to 120°, and particularly preferably 75° to 110°. If the contact angle immediately after application is within the above range, the resin composition will be impregnated into the surface of the fiber assembly and will be unevenly distributed on the outer surface, which will tend to improve water repellency. In a fiber-resin composite, the contact angle measured in an environment of 23°C and 50% humidity 30 seconds after a water droplet is dropped is 55° to 150°, preferably 60° to 120°, and more preferably 60° to 100°. If the contact angle after 30 seconds is within the above range, the resin composition is unevenly distributed on the outer surface of the short fiber aggregate, which tends to improve water repellency, and water droplets do not penetrate into the short fiber aggregate, which can suppress a decrease in mechanical strength due to fraying of the short fiber aggregate over the long term. In a fiber-resin composite, the absolute value of the Δcontact angle, which is the difference between the contact angle measured immediately after a water droplet is dropped and that measured 30 seconds later in an environment of 23°C and 50% humidity, is from 1 to 10, preferably from 2 to 10, and more preferably from 3 to 10. When the absolute value of the Δcontact angle is within the above range, the resin composition penetrates into the outer surface of the fiber aggregate and is unevenly distributed, so that the water droplets do not penetrate into the short fiber aggregate, and a decrease in mechanical strength due to long-term fraying of the short fiber aggregate can be suppressed. In the case of a fiber-resin composite, the tensile breaking elongation measured in accordance with JIS K7127 under conditions of a chuck distance of 50 mm, a pulling speed of 200 mm / min, and 23°C is 5% or less, or no break occurs. Preferably, the tensile breaking elongation is 3% or less, or no judgment is made, and more preferably, it is 1% or less, or no break occurs. If the tensile breaking elongation is within the above range, the resin composition can penetrate all the way to the outer surface of the fiber assembly, and sufficient strength can be obtained. In this specification, "a tensile breaking elongation of 5% or less" is also referred to as "non-stretchable."

[0013] [Short fiber sheet aggregate (Y)] A staple fiber aggregate is a sheet-like aggregate formed by aggregating a plurality of staple fibers in a regular or irregular manner. Therefore, not only those produced by entangling plant fibers and then skimming them, but also those produced by entangling non-plant natural fibers or chemical fibers without weaving, such as nonwoven fabrics, fall under the category of staple fiber aggregate. Examples of short fibers include carbon fibers, glass fibers, aramid fibers, alumina fibers, polypropylene fibers, polyamide fibers, polyester fibers, polyurethane fibers, silicon carbide fibers, boron fibers, metal fibers, and cellulose fibers. The short fibers can be used alone or in combination of two or more types. The short fibers are preferably polypropylene fibers, polyester fibers, or cellulose fibers, and more preferably cellulose fibers. Cellulose fibers are less likely to cause wrinkles, bending marks, or dents when the fiber-resin composite is bent or subjected to a load, and any wrinkles, bending marks, or dents that do occur tend to disappear over time, and furthermore, the design properties of the fiber-resin composite can be improved. Examples of cellulose fibers include hemp fibers, bamboo fibers, cotton fibers, wood fibers, kenaf fibers, hemp fibers, jute fibers, banana fibers, and coconut fibers. Examples of wood fibers include fibers obtained from wood pulp. Examples of wood include coniferous trees and broad-leaved trees. Cellulose fibers may be natural fibers or regenerated cellulose fibers. Cellulose fibers may be cellulose nanofibers. Cellulose fibers may be used alone or in combination of two or more types. Short fiber aggregates can be obtained by forming a fiber material containing fibers into a sheet. There are no particular limitations on the method for forming a fiber material into a sheet, and examples include weaving using spun yarn, needle punching used in the manufacture of various nonwoven fabrics, papermaking, and papermaking methods for making paper such as Japanese paper. Japanese paper made from fibers obtained from plants such as kozo (paper mulberry), mitsumata (Japanese mulberry), and gampi (Japanese mulberry bark) can be used.

[0014] The average thickness of the short fiber aggregate is, for example, 3 μm or more, preferably 5 μm or more, and more preferably 10 μm or more. The average thickness of the short fiber aggregate is, for example, 500 μm or less, preferably 250 μm or less, more preferably 200 μm or less, and particularly preferably 100 μm or less.

[0015] The weight of the short fiber aggregate is 5g / m 2 More than 80g / m 2 Preferably, it is 5 g / m or less. 2 More than 70g / m 2 More preferably, it is 5 g / m or less. 2 More than 50g / m 2 It is more preferable that the basis weight is not more than 100%. If the basis weight is within this range, the water repellency and resistance to water penetration of the fiber resin composite tend to be improved. Note that the basis weight of the short fiber aggregate means the total basis weight when a fiber resin composite is produced using a plurality of short fiber aggregates. The average fiber length of the short fibers constituting the short fiber aggregate is 2 mm to 30 mm, preferably 3 mm to 20 mm, and more preferably 3 mm to 15 mm. If the fiber length is within this range, the flexibility of the fiber-resin composite sheet tends to be improved. The short fiber aggregate may be coated in advance with an adhesive (also called a binder or a filler) that prevents the fibers from fraying together, as long as the desired effect is not impaired.

[0016] [Resin composition] The fiber-resin composite of the present embodiment includes a resin composition containing a 4-methyl-1-pentene copolymer (A). The 4-methyl-1-pentene copolymer (A), other polymers, and other components that may be included in the resin composition will be described below. <4-methyl-1-pentene copolymer (A)> The 4-methyl-1-pentene copolymer (A) satisfies the following requirement (Aa): In addition, it is preferable that the copolymer further satisfies one or more of the following requirements (Ab) to (Ac). A 4-methyl-1-pentene copolymer (A) that satisfies the following requirements enhances the stress relaxation and water repellency of a resin composition. Therefore, the 4-methyl-1-pentene copolymer (A) slowly flows the resin composition to return it to its original shape after the fiber-resin composite is bent or subjected to further load. As a result, the 4-methyl-1-pentene copolymer (A) eliminates wrinkles, creases, and dents caused by the bending or load over time. A resin composition containing a 4-methyl-1-pentene copolymer (A) that satisfies the following requirements easily penetrates into minute irregularities present on the surface of a short fiber aggregate, and therefore easily adheres to the short fiber aggregate even if the 4-methyl-1-pentene copolymer (A) does not have polar moieties. In addition, a resin composition containing a 4-methyl-1-pentene copolymer (A) that satisfies the following requirements easily penetrates into the minute irregularities present on the outer surface of a short fiber aggregate and has water repellency, so that when it is unevenly distributed in a short end fiber aggregate, it imparts water repellency and prevents water from penetrating into the interior of the short fiber aggregate.

[0017] [Requirements (Aa)] The 4-methyl-1-pentene copolymer (A) has a content of structural units (P) derived from 4-methyl-1-pentene of 65 mol% or more and less than 90 mol%, and a content of structural units (AQ) derived from ethylene or a linear or branched α-olefin having from 3 to 20 carbon atoms other than 4-methyl-1-pentene of more than 10 mol% and not more than 35 mol%. The content of the structural unit (P) is from 65 mol% to less than 90 mol%, and from the viewpoint of making it easier for wrinkles, bending marks, and dents caused by bending or loading to disappear over time, the content is preferably from 68 mol% to less than 90 mol%, more preferably from 68 mol% to less than 88 mol%, and particularly preferably from 68 mol% to less than 80 mol%. The content of the structural unit (AQ) (when there are two or more types of structural unit (AQ), the total content of said two or more types) is more than 10 mol% and not more than 35 mol%, and from the viewpoint of making it easier to eliminate wrinkles, bending marks, and dents that occur due to bending or load over time, it is preferably more than 10 mol% and not more than 32 mol%, more preferably more than 12 mol% and not more than 32 mol%, and particularly preferably more than 20 mol% and not more than 32 mol%. From the viewpoint of reducing the anisotropy of tensile elongation at break and the anisotropy of tear strength, the linear or branched α-olefin having 3 to 20 carbon atoms other than ethylene and 4-methyl-1-pentene that forms the structural unit (AQ) is preferably ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-hexadecene, or 1-octadecene, more preferably ethylene or an α-olefin having 3 to 4 carbon atoms, i.e., ethylene, propylene, or 1-butene, and particularly preferably propylene. In other words, the structural unit (AQ) is preferably a structural unit derived from ethylene or an α-olefin having 3 to 4 carbon atoms, and particularly preferably a structural unit derived from propylene.

[0018] Furthermore, when ethylene or a linear or branched α-olefin having from 3 to 20 carbon atoms is used as the monomer derived from the structural unit (AQ), the flexibility and relaxability of the resulting fiber-resin composite sheet are improved. The ethylene and linear or branched α-olefin derived from the structural unit (AQ) may be used alone or in combination of two or more types.

[0019] The 4-methyl-1-pentene copolymer (A) may contain other structural units besides the structural units (P) derived from 4-methyl-1-pentene and the structural units (AQ) derived from ethylene or a linear or branched α-olefin having from 3 to 20 carbon atoms other than 4-methyl-1-pentene, within a range that does not impair the desired effects. The content of the other structural units is, for example, 0 to 10 mol %. Monomers from which the above other structural units are derived include cyclic olefins, aromatic vinyl compounds, conjugated dienes, non-conjugated polyenes, functional vinyl compounds, hydroxyl group-containing olefins, halogenated olefins, and the like. Examples of the cyclic olefin, aromatic vinyl compound, conjugated diene, non-conjugated polyene, functional vinyl compound, hydroxyl group-containing olefin, and halogenated olefin that can be used include the compounds described in paragraphs 0035 to 0041 of JP-A No. 2013-169685. As the monomer that forms the other structural units, vinylcyclohexane and styrene are particularly preferred. When the 4-methyl-1-pentene copolymer (A) contains the other structural units, it may contain only one type of the other structural units, or it may contain two or more types of the other structural units. The content (mol %) of each structural unit in the 4-methyl-1-pentene copolymer (A) is measured by a 13C-NMR measurement method under the conditions described in the examples below.

[0020] [Requirements (Ab)] In the measurement of the 4-methyl-1-pentene copolymer (A) by differential scanning calorimetry (DSC), the melting point (Tm) is not observed or is in the range of 100°C to 199°C. It is preferable that the above melting point (Tm) of the 4-methyl-1-pentene copolymer (A) is not observed. When the melting point (Tm) of the 4-methyl-1-pentene copolymer (A) is within the above range, the fiber-resin composite sheet becomes more flexible and is less likely to crack or break when bent. When the melting point (Tm) of the 4-methyl-1-pentene copolymer (A) is not observed, the fiber-resin composite sheet is even less likely to crack or break when bent.

[0021] [Requirements (Ac)] The 4-methyl-1-pentene polymer (A) has a peak temperature of loss tangent tanδ (hereinafter also referred to as "tanδ peak temperature") of 15°C to 45°C as determined by dynamic viscoelasticity measurement at a frequency of 10 rad / s (1.6 Hz) in a temperature range of -40 to 150°C. The tan δ peak temperature of the 4-methyl-1-pentene polymer (A) is more preferably from 20°C to 45°C, and further preferably from 25°C to 45°C. When the tan δ peak temperature of the 4-methyl-1-pentene polymer (A) is within the above range, the fiber-resin composite has high room temperature relaxability, and therefore the fiber-resin composite is likely to slowly return to its original shape after being bent or subjected to further load when used at room temperature, and wrinkles, bend marks, and dents when used at room temperature are likely to disappear over time.

[0022] [Requirements (Ad)] The 4-methyl-1-pentene polymer (A) has a maximum value of loss tangent tanδ (hereinafter also referred to as "peak tanδ") of 1.0 to 5.0, which is obtained by measuring dynamic viscoelasticity in a temperature range of -40 to 150°C at a frequency of 10 rad / s (1.6 Hz). The tan δ peak temperature of the 4-methyl-1-pentene polymer (A) is preferably 1.5 to 5.0, more preferably 2.0 to 4.0. When the tan δ peak temperature of the 4-methyl-1-pentene polymer (A) is within the above range, wrinkles, bending marks, and dents in the fiber-resin composite tend to disappear over time during use, particularly after a long period of time has passed. The 4-methyl-1-pentene copolymer (A) preferably satisfies one or more of the following requirements (Ae) to (Ah), more preferably satisfies two or more of the requirements (Ae) to (Ah), and particularly preferably satisfies all of the requirements (Ae) to (Ah).

[0023] [Requirements (Ae)] The 4-methyl-1-pentene copolymer (A) has an intrinsic viscosity [η] measured in a decalin solvent at 135° C. of 0.5 to 4.0 dl / g. The intrinsic viscosity [η] of the 4-methyl-1-pentene copolymer (A) is more preferably 0.5 dl / g to 3.5 dl / g, and further preferably 1.0 dl / g to 3.5 dl / g. When the intrinsic viscosity [η] of the 4-methyl-1-pentene copolymer (A) is within the above range, the moldability of the fiber resin composite is good. The intrinsic viscosity [η] of the 4-methyl-1-pentene copolymer (A) is a value measured by the method described in the examples below.

[0024] Requirements The molecular weight distribution (Mw / Mn) of the 4-methyl-1-pentene copolymer (A) is 1.0 to 3.5. The Mw / Mn of the 4-methyl-1-pentene copolymer (A) is more preferably 1.1 to 3.0. When the Mw / Mn of the 4-methyl-1-pentene copolymer (A) is in the above range, the fiber-resin composite is less likely to become sticky and the appearance of the fiber-resin composite is likely to be good. From the viewpoint of improving the moldability of the composition, the weight-average molecular weight (Mw) of the 4-methyl-1-pentene copolymer (A) is 1×10 4 ~2×10 6 Preferably, it is 1×10 4 ~1×10 6 It is more preferable that: The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the 4-methyl-1-pentene copolymer (A) are values ​​calculated by the method described in the examples below.

[0025] [Requirements (Ag)] The density of 4-methyl-1-pentene copolymer (A) measured in accordance with JIS K7112-2:2023 (density gradient tube method) is 830 kg / m from the viewpoint of handling. 3 ~860kg / m 3 is. The density of the 4-methyl-1-pentene copolymer (A) is 830 kg / m 3 ~850kg / m 3 When the density of the 4-methyl-1-pentene copolymer (A) is within the above range, the water repellency of the fiber-resin composite is improved.

[0026] [Requirements (Ah)] The melt flow rate (MFR) of the 4-methyl-1-pentene copolymer (A), measured in accordance with ASTM D1238 at 230°C under a load of 2.16 kg or at 260°C under a load of 5.0 kg, is preferably 0.1 g / 10 min to 100 g / 10 min, more preferably 0.5 g / 10 min to 50 g / 10 min, and even more preferably 0.5 g / 10 min to 30 g / 10 min, from the viewpoint of providing a fiber-resin composite sheet with excellent fuzz resistance and excellent resistance to crease and wrinkle recovery. When the 4-methyl-1-pentene copolymer (A) has an MFR within the above range, fuzz is less likely to occur on the cut surface of the fiber-resin composite, and even when the fiber-resin composite is bent or subjected to a load, wrinkles, bend marks, and dents are less likely to appear on the surface, and even if they do appear, they tend to disappear over time.

[0027] (Method for producing 4-methyl-1-pentene copolymer (A)) The method for producing the 4-methyl-1-pentene copolymer (A) is not particularly limited, but it can be produced, for example, by polymerizing 4-methyl-1-pentene with the above-mentioned ethylene or a linear or branched α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) in the presence of an appropriate polymerization catalyst such as a magnesium-supported titanium catalyst or a metallocene catalyst. Suitable polymerization catalysts that can be used here include conventionally known catalysts, such as magnesium-supported titanium catalysts and metallocene catalysts described in International Publication Nos. 01 / 53369, 01 / 27124, JP-A-3-193796, JP-A-2-41303, WO 2011 / 055803, WO 2014 / 050817, etc. Polymerization can be carried out by a method appropriately selected from liquid phase polymerization methods including solution polymerization and suspension polymerization, gas phase polymerization methods, etc.

[0028] In the liquid phase polymerization method, an inert hydrocarbon solvent can be used as a solvent constituting the liquid phase. Examples of the inert hydrocarbon include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene, alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane, and methylcyclohexane, aromatic hydrocarbons such as benzene, toluene, and xylene, halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane, trichloromethane, and tetrachloromethane, and mixtures thereof.

[0029] Furthermore, in the liquid phase polymerization method, bulk polymerization can also be performed using a monomer corresponding to the structural unit (P) derived from the aforementioned 4-methyl-1-pentene (i.e., 4-methyl-1-pentene), or a monomer corresponding to the structural unit (AQ) derived from the aforementioned ethylene or a linear or branched α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) (i.e., the aforementioned ethylene or a linear or branched α-olefin having 3 to 20 carbon atoms (4-methyl-1-pentene) itself as the solvent. Furthermore, by copolymerizing the above 4-methyl-1-pentene with the above ethylene or a linear or branched α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) in a stepwise manner, it is also possible to appropriately control the composition distribution of the structural units (P) derived from 4-methyl-1-pentene and the structural units (AQ) derived from ethylene or a linear or branched α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) that constitute the 4-methyl-1-pentene copolymer (A).

[0030] The polymerization temperature is preferably −50 to 200° C., more preferably 0 to 100° C., and further preferably 20 to 100° C. The polymerization pressure is preferably normal pressure to 10 MPa gauge pressure, and more preferably normal pressure to 5 MPa gauge pressure. During polymerization, hydrogen may be added for the purpose of controlling the molecular weight and polymerization activity of the resulting polymer. The amount of hydrogen to be added is suitably about 0.001 to 100 nL per 1 kg of the total amount of the 4-methyl-1-pentene and the ethylene or linear or branched α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene).

[0031] (4-methyl-1-pentene copolymer (A) content) The content of the 4-methyl-1-pentene copolymer (A) is preferably 30% by mass or more and 100% by mass or less, more preferably 50% by mass or more and 100% by mass or less, and even more preferably 60% by mass or more and 100% by mass or less, based on the total mass of the resin composition. When the content of the 4-methyl-1-pentene copolymer (A) is within the above range, wrinkles, bending marks, and dents that occur when the fiber-resin composite is bent or subjected to a load tend to disappear over time, and the water repellency of the fiber-resin composite tends to improve.

[0032] <Other polymers (B)> The fiber-resin composite of this embodiment may contain, in addition to the 4-methyl-1-pentene copolymer (A), other polymers (hereinafter referred to as "other polymers (B)") to the extent that the desired effects are not impaired. Examples of other polymers include thermoplastic polyolefin resins such as low-density polyethylene, medium-density polyethylene, high-density polyethylene, high-pressure low-density polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene (excluding 4-methyl-1-pentene copolymers satisfying requirement (Aa)), poly-3-methyl-1-butene, ethylene-α-olefin copolymer, propylene-α-olefin copolymer, 1-butene-α-olefin copolymer, cyclic olefin copolymer, and chlorinated polyolefin; thermoplastic polyamide resins such as aliphatic polyamides (nylon 6, nylon 11, nylon 12, nylon 66, nylon 610, and nylon 612) and polyether-block amide copolymers; thermoplastic polyester resins such as polyethylene terephthalate and polybutylene terephthalate; polystyrene; ABS resin; and AS. Thermoplastic vinyl aromatic resins such as vinyl chloride resin, vinylidene chloride resin, acrylic resin, ethylene-vinyl acetate copolymer, ethylene-(meth)acrylate copolymer, ionomer, ethylene-vinyl alcohol copolymer, polyvinyl alcohol, polyvinyl fluoride resin, polytetrafluoroethylene, polyvinylidene fluoride, fluororesins such as ETFE, polycarbonate, polyacetal, polyphenylene oxide, polyphenylene sulfide, polyimide, polyarylate, polysulfone, polyethersulfone, rosin resin, terpene resin, and thermoplastic elastomers such as petroleum resin olefin elastomer, styrene elastomer, acid-modified styrene elastomer, vinyl chloride elastomer, urethane elastomer, ester elastomer, amide elastomer, etc. These resins may be used alone or in combination of two or more. The other polymer (B) is preferably a thermoplastic elastomer, more preferably an olefin-based elastomer (B-1) or a styrene-based elastomer (B-2), and even more preferably a styrene-based elastomer (B-2).

[0033] (Olefin elastomer (B-1)) A first embodiment of the olefin elastomer (B-1) includes a copolymer of ethylene or propylene with butadiene, hydrogenated butadiene, isoprene, hydrogenated isoprene isobutylene, or an α-olefin. The copolymerization may be in the form of block copolymerization or graft copolymerization, but a copolymer consisting of ethylene or propylene and an α-olefin may be a random copolymer. As the α-olefin, 1-butene, 1-octene, etc. are preferably used. Examples of the olefin-based elastomer (B-1) include block copolymers of a polyolefin block that forms a highly crystalline polymer such as polypropylene, which serves as the hard portion, and an amorphous monomer copolymer that serves as the soft portion. Specific examples include an olefin (crystalline)-ethylene-butylene-olefin block copolymer and a propylene-olefin (amorphous)-propylene block copolymer. Specific examples of the first aspect of the olefin-based elastomer (B-1) include those commercially available from ENEOS Materials Corporation under the trade name DYNARON (registered trademark), from Mitsui Chemicals, Inc. under the trade names TAFMER (registered trademark) and NOTIO (registered trademark), from The Dow Chemical Company under the trade names ENGAGE (registered trademark) and VERSIFY (registered trademark), and from ExxonMobil Chemical Corporation under the trade name Vistamaxx (registered trademark).

[0034] A second embodiment of the olefinic elastomer (B-1) is a blend of one selected from the group consisting of polyethylene and polypropylene with one selected from the group consisting of ethylene-propylene copolymer, ethylene-propylene-diene copolymer, ethylene-butene copolymer, and hydrogenated styrene-butadiene. Such a blend is preferably one in which the partially or completely crosslinked ethylene-propylene copolymer, ethylene-propylene-diene copolymer, or ethylene-butene copolymer exists as an island phase in a phase selected from the group consisting of polyethylene and polypropylene by blending in the presence of a crosslinking agent. Specific examples of the second embodiment of the olefin-based elastomer (B-1) include those commercially available from Mitsui Chemicals, Inc. under the trade name: Milastomer (registered trademark), from Sumitomo Chemical Co., Ltd. under the trade name: Esporex (registered trademark), from Mitsubishi Chemical Corporation under the trade name: Thermorun (registered trademark) and Zelas (registered trademark), and from Celanese Corporation under the trade name: Santoplene (registered trademark). The olefinic elastomer (B-1) may be modified to have an acid anhydride group, a carboxyl group, an amino group, an imino group, an alkoxysilyl group, a silanol group, a silyl ether group, a hydroxyl group, or an epoxy group.

[0035] (Styrene-based elastomer (B-2)) Examples of styrene-based elastomers (B-2) include block copolymers (SBS) of polystyrene blocks that form the hard portion (crystalline portion) and diene monomer blocks that form the soft portion, hydrogenated styrene-butadiene-styrene block copolymers (HSBR), styrene-ethylene-propylene-styrene block copolymers (SEPS), styrene-ethylene-butene-styrene block copolymers (SEBS), styrene-isoprene-styrene block copolymers (SIS), styrene-isobutylene-styrene copolymers (SIBS), and styrene-isobutylene copolymers (SIB). The styrene-based elastomer (B-2) may be used alone or in combination of two or more kinds. A specific example of the hydrogenated styrene-butadiene-styrene block copolymer (HSBR) is one commercially available from ENEOS Materials Corporation under the trade name Dynaron (registered trademark). Styrene-ethylene-propylene-styrene block copolymer (SEPS) is obtained by hydrogenating styrene-isoprene-styrene block copolymer (SIS). Specific examples of SIS include those commercially available from ENEOS Materials Corporation under the trade name JSR SIS (registered trademark), Kuraray Co., Ltd. under the trade name Hybler (registered trademark), and Kraton Polymers Co., Ltd. under the trade name Kraton D (registered trademark).

[0036] Specific examples of styrene-ethylene-propylene-styrene block copolymers (SEPS) include those commercially available from Kuraray Co., Ltd. under the trade name: Septon (registered trademark) or from Kraton Polymers Co., Ltd. under the trade name: Kraton (registered trademark). Specific examples of styrene-ethylene-butene-styrene block copolymers (SEBS) include those commercially available from Asahi Kasei Corporation under the trade name Tuftec (registered trademark) or Kraton Polymers Co., Ltd. under the trade name Kraton (registered trademark).

[0037] Specific examples of styrene-isobutylene copolymer (SIB) and styrene-isobutylene-styrene copolymer (SIBS) include those commercially available from Kaneka Corporation under the trade name: SIBSTAR (registered trademark). Furthermore, among the styrene-based elastomers (B-2), vinyl SIS (product name: Hybler, brand 5127) and vinyl SEPS (product name: Hybler, brand 7125) manufactured by Kuraray Co., Ltd., and SEBS (product name: SOE, brands: S1605, S1611, and L609) manufactured by Asahi Kasei Corporation, which have moderate compatibility with the 4-methyl-1-pentene copolymer (A), can also be preferably used from the viewpoints of compatibility, the temperature range in which the loss tangent shows a maximum value, and the magnitude of the maximum value of the loss tangent.

[0038] (Content of other polymers (B)) The content of the other polymer (B) is not particularly limited, but is preferably 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 2% by mass or more, still more preferably 3% by mass or more, and is preferably 65% ​​by mass or less, more preferably 60% by mass or less, even more preferably 55% by mass or less, even more preferably 50% by mass or less, particularly preferably 45% by mass or less, based on 100 parts by mass of the total of (A) and the other polymer (B). It is preferably 0.5 to 65% by mass, more preferably 0.5 to 60% by mass, even more preferably 1 to 55% by mass, even more preferably 2 to 50% by mass, particularly preferably 3 to 45% by mass. When the content of the thermoplastic elastomer is within the above range, flexibility at room temperature and toughness at low temperatures are improved, so that the fiber-resin composite can have a better feel immediately after touching.

[0039] <Other ingredients> In addition to the 4-methyl-1-pentene polymer (A) and the other polymer (B), the fiber-resin composite of the present embodiment may contain components other than the 4-methyl-1-pentene polymer (A) and the other polymer (B) (hereinafter also referred to as "other components") depending on the application, within a range that does not impair the desired effects. Examples of such resin additives include pigments, dyes, fillers, lubricants, plasticizers, release agents, antioxidants, flame retardants, UV absorbers, antibacterial agents, surfactants, antistatic agents, weather stabilizers, heat stabilizers, antislip agents, antiblocking agents, foaming agents, crystallization aids, antifogging agents, (transparent) nucleating agents, antioxidants, hydrochloric acid absorbers, impact modifiers, crosslinking agents, co-crosslinking agents, crosslinking aids, adhesives, softeners, processing aids, etc. These additives can be used alone or in appropriate combinations of two or more. Examples of pigments include inorganic pigments (titanium oxide, iron oxide, chromium oxide, cadmium sulfide, etc.) and organic pigments (azo lake pigments, thioindigo pigments, phthalocyanine pigments, anthraquinone pigments). Examples of dyes include azo pigments, anthraquinone pigments, triphenylmethane pigments, etc. The content of these pigments and dyes is not particularly limited, but is preferably 5% by mass or less, and more preferably 0.1 to 3% by mass, in total, based on the total mass of the 4-methyl-1-pentene polymer (A).

[0040] Examples of fillers include glass fiber, carbon fiber, silica fiber, metal (stainless steel, aluminum, titanium, copper, etc.) fiber, carbon black, silica, glass beads, silicates (calcium silicate, talc, clay, etc.), metal oxides (iron oxide, titanium oxide, alumina, etc.), metal carbonates (calcium sulfate, barium sulfate), various metal (magnesium, silicon, aluminum, titanium, copper, etc.) powders, mica, glass flakes, etc. These fillers may be used alone or in combination of two or more. Examples of lubricants include waxes (such as carnauba wax), higher fatty acids (such as stearic acid), higher alcohols (such as stearyl alcohol), and higher fatty acid amides (such as stearic acid amide). Examples of the plasticizer include aromatic carboxylic acid esters (dibutyl phthalate, etc.), aliphatic carboxylic acid esters (acetyl ricinoleate, etc.), aliphatic dialkoxy esters (adipic acid-propylene glycol polyester, etc.), aliphatic tricarboxylic acid esters (triethyl citrate, etc.), phosphate triesters (triphenyl phosphate, etc.), epoxy fatty acid esters (epoxybutyl stearate, etc.), and petroleum resins.

[0041] Examples of the release agent include lower (C1-4) alcohol esters of higher fatty acids (butyl stearate, etc.), polyhydric alcohol esters of fatty acids (C4-30) (hardened castor oil, etc.), glycol esters of fatty acids, and liquid paraffin. Examples of antioxidants include phenol-based (2,6-di-t-butyl-4-methyl-phenol, etc.), polycyclic phenol-based (2,2'-methylenebis(4-methyl-6-t-butylphenol, etc.)), phosphorus-based (tetrakis(2,4-di-t-butylphenyl)-4,4-biphenylenediphosphonate, etc.), and amine-based (N,N-diisopropyl-p-phenylenediamine, etc.) antioxidants. Examples of the flame retardant include organic flame retardants (nitrogen-containing, sulfur-containing, silicon-containing, phosphorus-containing, etc.) and inorganic flame retardants (antimony trioxide, magnesium hydroxide, zinc borate, red phosphorus, etc.). Examples of ultraviolet absorbers include benzotriazole-based, benzophenone-based, salicylic acid-based, and acrylate-based ones.

[0042] Examples of antibacterial agents include quaternary ammonium salts, pyridine compounds, organic acids, organic acid esters, halogenated phenols, and organic iodines. The surfactants may include nonionic, anionic, cationic or amphoteric surfactants. Examples of nonionic surfactants include polyethylene glycol-based nonionic surfactants such as higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, and polypropylene glycol ethylene oxide adducts; polyhydric alcohol-based nonionic surfactants such as polyethylene oxide, fatty acid esters of glycerin, fatty acid esters of pentaerythritol, fatty acid esters of sorbitol or sorbitan, alkyl ethers of polyhydric alcohols, and fatty amides of alkanolamines. Examples of anionic surfactants include sulfate ester salts such as alkali metal salts of higher fatty acids; sulfonates such as alkylbenzene sulfonates, alkyl sulfonates, and paraffin sulfonates; and phosphate ester salts such as higher alcohol phosphate ester salts. Examples of cationic surfactants include quaternary ammonium salts such as alkyltrimethylammonium salts. Examples of amphoteric surfactants include amino acid-based amphoteric surfactants such as higher alkylaminopropionates; and betaine-based amphoteric surfactants such as higher alkyldimethylbetaines and higher alkyldihydroxyethylbetaines. Examples of the antistatic agent include the above-mentioned surfactants, fatty acid esters, and polymeric antistatic agents. Examples of the fatty acid esters include esters of stearic acid and oleic acid, and examples of the polymeric antistatic agents include polyether ester amides. The content of the various additives such as the filler, lubricant, plasticizer, mold release agent, antioxidant, flame retardant, UV absorber, antibacterial agent, surfactant, and antistatic agent is not particularly limited depending on the application within a range that does not impair the object of the present invention, but is preferably 0.1 to 30 mass% in total relative to the total mass of the 4-methyl-1-pentene polymer (A).

[0043] <Method of manufacturing fiber-resin composite> Another embodiment of the present invention is a method for producing a method for manufacturing a semiconductor device comprising the steps of: Total basis weight: 5g / m 2 More than 80g / m 2preparing one or more sheet-like short fiber aggregates having an average fiber length of 2 mm or more and 30 mm or less; The following requirements (Aa): (Aa) the content of structural units (P) derived from 4-methyl-1-pentene is 65 mol% or more and less than 90 mol%, and the content of structural units (AQ) derived from monomers selected from the group consisting of ethylene and linear or branched α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is more than 10 mol% and 35 mol% or less; preparing one or more sheet-shaped resin compositions containing a 4-methyl-1-pentene copolymer (A) that satisfies the above formula: a step of stacking the sheet-like short fiber aggregate and one sheet-like resin composition when the sheet-like short fiber aggregate is single, or sandwiching the single sheet-like resin composition between the plurality of sheet-like short fiber aggregates when the sheet-like short fiber aggregate is multiple, and hot pressing the resulting mixture; The method for producing the fiber-resin composite includes:

[0044] The fiber-resin composite of this embodiment can be produced by heating and pressing a sheet or film of a resin composition containing the 4-methyl-1-pentene copolymer (A) and a sheet-like short fiber aggregate together using a known heat-pressing device. Sheets or films of resin compositions containing 4-methyl-1-pentene copolymer (A) can be produced by known methods without particular limitations. For example, they can be obtained by molding using a general T-die extrusion molding machine or mold printing molding machine. For example, a sheet is formed by molding using a single-screw extruder at a cylinder temperature of 170 to 250°C and a cast roll temperature of 0 to 70°C. The thickness of the sheet is usually 5 to 1000 μm, preferably 10 to 500 μm, more preferably 40 to 500 μm, even more preferably 80 to 500 μm, and particularly preferably 120 to 300 μm. A thickness within this range ensures excellent sheet productivity, prevents pinholes from forming during sheet molding, and provides sufficient strength. The sheet surface may be embossed, or the sheet may be stretched during or after molding. Furthermore, the molded sheet may be annealed at a temperature of less than 100°C to remove residual strain on the sheet.

[0045] Examples of a thermocompression device for press-bonding and heating a sheet or film of a resin composition containing 4-methyl-1-pentene copolymer (A) and a sheet-like short fiber aggregate include an autoclave and a heat press. The compression bonding conditions and heating conditions are set appropriately depending on the purpose and application. The compression bonding pressure is, for example, 0.1 MPa or more, preferably 0.5 MPa or more. The compression bonding pressure is, for example, 5.0 MPa or less, preferably 2.5 MPa or less. The heating temperature is, for example, 100°C or more, preferably 120°C or more, and for example, 300°C or less, preferably 240°C or less. The compression bonding time and heating time are, for example, 0.5 minutes or more, preferably 1 minute or more. The compression bonding time and heating time are, for example, 30 minutes or less, preferably 10 minutes or less. The environmental conditions for the pressure bonding and heating may be a normal pressure environment or a reduced pressure environment. The reduced pressure environment includes a vacuum environment. A reduced pressure environment is preferable as the environmental condition. A reduced pressure environment can suppress the generation of bubbles in the fiber-resin composite sheet. This melts the resin composition containing the 4-methyl-1-pentene copolymer (A), and the short fiber aggregate is impregnated with the resin composition containing the thermoplastic 4-methyl-1-pentene copolymer (A). Thereafter, the resin composition containing the 4-methyl-1-pentene copolymer (A) is cooled to room temperature. This results in a fiber-resin composite in which the resin composition has penetrated all the way to the surface of the fiber aggregate.

[0046] In the above method, a sheet or film of the resin composition containing the 4-methyl-1-pentene copolymer (A) can be placed on only one side of the fiber assembly, and then pressed and heated. In this case, the resin composition containing the 4-methyl-1-pentene copolymer (A) penetrates to a predetermined depth from one surface to the other surface in the thickness direction of the short fiber assembly. In this case, the resin composition containing 4-methyl-1-pentene copolymer (A) may or may not reach from one surface to the other surface in the thickness direction of the short fiber aggregate. The penetration depth of the resin composition containing 4-methyl-1-pentene copolymer (A) in the thickness direction of the short fiber aggregate is appropriately set depending on the thickness of the sheet or film of the resin composition containing 4-methyl-1-pentene copolymer (A), the thickness of the sheet-like short fiber aggregate, and the heating pressure, temperature conditions, etc. during compression bonding. In other words, the resin composition containing the 4-methyl-1-pentene copolymer (A) may be impregnated from one surface in the thickness direction of the short fiber aggregate to a predetermined depth, and the other surface in the thickness direction of the short fiber aggregate may not be impregnated with the resin composition containing the 4-methyl-1-pentene copolymer (A).

[0047] From the viewpoints of improving the recovery property of the fiber-resin composite when it is bent and making it difficult for wrinkles, bending marks, and dents to occur when the fiber-resin composite is bent or a load is applied, it is preferable that the short fiber aggregate has an area inside in the thickness direction or on the other surface side that is not impregnated with the resin composition containing 4-methyl-1-pentene copolymer (A). The impregnation state of the resin composition containing 4-methyl-1-pentene copolymer (A) can be confirmed, for example, by observing a cross section of the fiber-resin composite with an optical microscope (OM) or a scanning electron microscope (SEM).

[0048] Furthermore, when pressure is applied, a release film can be placed on the outside of the sheet or film of the resin composition containing the 4-methyl-1-pentene copolymer (A). This improves workability and also allows for the production of a fiber-resin composite sheet with excellent appearance. Furthermore, the surface shape of the release film can be processed as desired. For example, the surface of the release film can be textured. This improves the appearance of the fiber-resin composite sheet.

[0049] The fiber-resin composite of this embodiment is cured as necessary. The curing temperature is, for example, 40°C or higher, preferably 80°C or higher. The curing temperature is, for example, 140°C or lower, preferably 120°C or lower. The curing time is, for example, 30 minutes or longer, preferably 1 hour or longer. The curing time is, for example, 7 days or shorter, preferably 3 days or shorter. Furthermore, the fiber-resin composite of this embodiment can have a coating layer formed on its surface to the extent that the functions of fluff resistance, flex recovery, crease resistance, and wrinkle recovery are not impaired. The coating layer can prevent swelling of the resin composition containing the 4-methyl-1-pentene copolymer (A) due to human sebum during use and wear degradation due to rubbing.

[0050] <Shapes and uses of fiber-resin composites> The fiber resin composite preferably has a basis weight of 100 g / m from the viewpoint of flexibility and impregnation during composite production. 2More than 250g / m 2 The following is the result. The fiber resin composite may have a thickness of 40 μm or more and 300 μm or less. The thickness of the fiber-resin composite sheet varies depending on its intended use, but for example, the lower limit of the thickness is 15 μm or more, preferably 30 μm or more, more preferably 40 μm or more, even more preferably 80 μm or more, and particularly preferably 120 μm or more. The upper limit of the thickness is, for example, 5000 μm or less, preferably 1000 μm or less, more preferably 500 μm or less, even more preferably 400 μm or less, and particularly preferably 300 μm or less. The surface of the fiber-resin composite sheet may be covered with a coating layer.

[0051] The fiber-resin composite of this embodiment may be molded into various shapes depending on the use form, application, etc., and may be attached to the surface of another molded body, stacked in sheet form and sewn, fused with heat, ultrasound, etc. to form a cylindrical or bag shape, or the laminate may be folded into various shapes such as a tray or bag. When the composite is folded into a shape, it is not sewn or fused, and can be refolded into a different shape, allowing for repeated use in various shapes, which is particularly preferable. Furthermore, the fiber-resin composite of this embodiment can be formed into a cylindrical, tray, or bag shape to serve as a cooler container for keeping wine, etc., cold by filling it with water.

[0052] The fiber-resin composite of this embodiment is suitable for use in various industrial fields, such as daily necessities such as sundries, toys, accessories, vehicles such as automotive interior materials, furniture, sports, robots, office supplies, architecture, healthcare, and electrical appliances. In the daily necessities field, examples include storage containers, insulated containers, and food storage containers. [Example]

[0053] The present invention will be specifically explained below with reference to examples and comparative examples, but the present invention is not limited to the following examples as long as it does not depart from the gist of the invention.

[0054] [Method for extracting short fiber aggregate and resin composition from fiber-resin composite] A fiber-resin composite sheet cut into a 100 x 100 cm square was immersed in 100 ml of toluene solvent at 60°C for 2 hours. After immersion, the sheet was removed and washed twice with toluene solution and once with methanol solution. It was then dried in a vacuum dryer at 80°C for 6 hours to extract the short fiber aggregate. The toluene solution was then poured into 1 L of acetone solvent to precipitate the resin composition. This composition was then dried in a vacuum dryer at 130°C for 12 hours, and the resin composition was then extracted.

[0054] [Methods for measuring various physical properties] First, the methods for measuring various physical properties used in the present examples will be described below. (1) Composition 13 The composition of the polymer was determined by C-NMR measurement. 13 The measurement conditions for C-NMR are as follows: [conditions] Measurement equipment: Nuclear magnetic resonance equipment (ECP500 type, manufactured by JEOL Ltd.) Observation kernel: 13 C(125MHz) Sequence: Single pulse proton decoupling Pulse width: 4.7 μsec (45° pulse) Repeat time: 5.5 seconds Accumulation count: 10,000 times or more Solvent: orthodichlorobenzene / deuterated benzene (volume ratio: 80 / 20) mixed solvent Sample concentration: 55 mg / 0.6 mL Measurement temperature: 120℃ Chemical shift reference value: 27.50 ppm

[0055] (2) Intrinsic viscosity [η] Approximately 20 mg of 4-methyl-1-pentene copolymer (A) was dissolved in 25 ml of decalin, and the specific viscosity ηsp was measured using an Ubbelohde viscometer in an oil bath at 135 °C. This decalin solution was diluted with 5 ml of decalin, and the specific viscosity ηsp was measured in the same manner as above. This dilution procedure was repeated two more times, and the value of ηsp / C when the concentration (C) was extrapolated to 0 was calculated as the limiting viscosity [η] (unit: dL / g) (see Equation 1 below). [η]=lim(ηsp / C) (C→0)...Equation 1

[0056] (3) Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) Liquid chromatograph: Waters ALC / GPC 150-C plus model (integrated differential refractometer detector) was used, and two Tosoh GMH6-HT and two GMH6-HTL columns were connected in series. Gel permeation chromatography (GPC) measurements were performed using o-dichlorobenzene as the mobile phase medium at a flow rate of 1.0 ml / min and 140°C. The weight-average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were determined by analyzing the obtained chromatogram using a calibration curve prepared using a standard polystyrene sample according to a known method.

[0057] (4) Density The density was determined in accordance with JIS K7112 (density gradient tube method).

[0058] (5) Melting point (Tm) Measurement was performed using a differential scanning calorimetry (DSC) according to the following method in accordance with JIS K7121. Approximately 5 mg of 4-methyl-1-pentene copolymer (A) was sealed at room temperature in an aluminum pan for measurement of a differential scanning calorimeter (DSC220C) manufactured by Seiko Instruments Inc. and heated from room temperature to 260°C at a rate of 10°C / min. To completely melt the 4-methyl-1-pentene copolymer (A), it was held at 260°C for 5 minutes and then cooled to -50°C at a rate of 10°C / min. After holding at -50°C for 5 minutes, it was heated a second time to 260°C at a rate of 10°C / min. The temperature at which a peak was observed during this second heating was taken as the melting point (Tm) of the polymer. If no clear peak was detected, it was considered to be no melting point. If multiple peaks were detected, the peak detected at the highest temperature was used.

[0059] (6) Melt flow rate (MFR) The melt flow rate (MFR) of the 4-methyl-1-pentene copolymer (A) was measured in accordance with ASTM D1238 at 230°C under a load of 2.16 kg and at 260°C under a load of 5.0 kg. The MFR of other polymers (B) (i.e., polymers B-1 and B-2 below) was measured under the measurement conditions of 230°C under a load of 2.16 kg.

[0060] (7) tanδ peak temperature, tanδ peak value For the dynamic viscoelasticity measurements, a 3mm thick pressed sheet was used as the measurement sample, and 45mm x 10mm x 3mm strips were cut out from it. Using an ANTON Paar MCR301, the temperature dependence of dynamic viscoelasticity was measured from -40 to 150°C at a frequency of 10 rad / s, and the temperature at which the loss tangent (tanδ) due to the glass transition temperature reached its peak value (maximum value) in the range of 0 to 40°C (tanδ peak temperature) and the loss tangent (tanδ) value at that time (tanδ peak value) were measured.

[0061] (8) Metsuke A 100mm x 100mm square short fiber aggregate was used as a test piece, and the mass (g) was measured using an electronic balance (manufactured by Kensei Kogyo Co., Ltd.). 2 Convert to mass (g) per unit, round off to the second decimal place, and calculate the basis weight [g / m 2 This procedure was repeated three times for each fiber assembly to determine the basis weight.

[0062] (9) Average fiber length Short fiber aggregates torn by hand into approximately 20 mm x 20 mm squares were dispersed in water, scooped up using black filter paper, and dried at 120°C for 12 hours. From the obtained measurement samples, fibers with visible ends were selected as much as possible, and the fiber length was determined by observing them with a stereomicroscope (Olympus SZX10, observation magnification 0.3-0.6) or an optical microscope (Nikon ECLIPSE-LV100POL, observation magnification x50). Approximately 50 fibers per sample were measured, and the average fiber length was calculated based on the minimum and maximum measured values.

[0063] [Preparing materials] <Synthesis of 4-methyl-1-pentene copolymer (A)> [Synthesis of 4-methyl-1-pentene copolymer (A-1)] A 1.5-liter stainless steel autoclave equipped with a stirrer and thoroughly purged with nitrogen was charged with 300 ml of normal hexane (dried over activated alumina in a dry nitrogen atmosphere) and 450 ml of 4-methyl-1-pentene at 23°C. 0.75 ml of a 1.0 mmol / ml toluene solution of triisobutylaluminum (TIBAL) was charged into the autoclave, and the stirrer was turned on. Next, the autoclave was heated to an internal temperature of 60°C and pressurized with propylene to a total pressure of 0.40 MPa (gauge pressure). Subsequently, 0.34 ml of a toluene solution containing 1 mmol of methylaluminoxane (calculated as Al) and 0.01 mmol of diphenylmethylene(1-ethyl-3-t-butylcyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride, which had been prepared in advance, was pressure-fed into the autoclave with nitrogen to initiate polymerization. During the polymerization reaction, the internal temperature of the autoclave was adjusted to 60°C. Sixty minutes after the start of polymerization, 5 ml of methanol was pressure-fed into the autoclave with nitrogen to terminate the polymerization, and the autoclave was depressurized to atmospheric pressure. Acetone was poured into the reaction solution with stirring. The obtained powdery polymer containing the solvent was dried at 100°C under reduced pressure for 12 hours to obtain 36.9 g of 4-methyl-1-pentene copolymer (A-1). The measurement results of various physical properties are shown in Table 1 below.

[0064] [Table 1]

[0065] <Other polymers (B)> (B-1): Styrene-vinylisoprene-styrene copolymer "Hybrar 7311F" (Kuraray Co., Ltd.)

[0066] <Short fiber aggregate> (Y-1): Cellulose fiber aggregate (washi paper), made in Gokayama Washi Village (paper mulberry fiber, handmade), basis weight: 65g / m 2 , average fiber length: 7 mm, average thickness: 200 μm (Y-2): Cellulose fiber aggregate (washi paper), made in Gokayama Washi Village (paper mulberry fiber, handmade), basis weight: 18g / m 2 , average fiber length: 7 mm, average thickness: 70 μm (Y-3): Cellulose fiber aggregate (washi paper), made in Gokayama Washi Village (paper mulberry fiber, machine-made), basis weight: 9.6 g / m 2 , average fiber length: 6 mm, average thickness: 40 μm (Y-4): Copy paper (AS ONE Corporation, 500 sheets, A4 size), basis weight: 68 g / m 2 , average fiber length: 1.5 mm, average thickness: 90 μm

[0067] [Evaluation of fiber-resin composite sheets] The fiber resin composites produced in the examples were evaluated according to the following criteria. <Tack suppression> A sheet sample measuring 152 mm x 100 mm was cut into 15 mm widths using a cutter. This sheet was folded 180° with the short fiber aggregate inner layer facing inward, and a 2 kg weight was placed on the sheet. After leaving it for 10 minutes, the weight was removed. The appearance of the sheet was observed immediately after removing the weight and 60 seconds later, and the tack-inhibiting properties were evaluated according to the following evaluation criteria. [Evaluation criteria] ×: Still stuck after 60 seconds △: Peeled off within 60 seconds 〇: The sheet peeled off immediately after removal and quickly returned to its original shape

[0068] <Stretchability> A 152 mm x 100 mm sheet sample was cut into 15 mm widths using a cutter. Measurements were performed using a tensile tester (Instron Universal Testing Machine 3380) in accordance with JIS K7127, with a chuck distance of 50 mm, a tensile speed of 200 mm / min, and a temperature of 23°C. If the resin stretched and broke, the tensile breaking elongation (%) was recorded. If only the fiber structure broke and then the resin layer stretched, the value (%) at which the fiber structure broke was recorded. If neither broke, the result was recorded as "no break."

[0069] <Water repellency> Using an automatic contact angle meter (CA-V type) and surface analysis software (FAMAS), the contact angle (°) was measured when a water droplet was dropped onto the inner layer of the resulting fiber-resin composite sheet at 23°C and 50% humidity. A larger contact angle indicates higher water repellency. The difference between the value immediately after dropping the water droplet and the value 30 seconds later was recorded as the absolute value of the Δcontact angle.

[0070] <Wrinkles, fold marks, dents> A 152 mm x 100 mm sheet sample was cut into 15 mm widths using a cutter. This sheet was folded 180° with the short fiber aggregate inner layer facing inward, and a 2 kg weight was placed on the sheet. After leaving it for 10 minutes, the weight was removed. The appearance of the sheet was observed immediately after removing the weight and 60 minutes later, and wrinkles, fold marks, and dents were visually checked using the following evaluation criteria. [Evaluation criteria] (i) 60 minutes after removing the weight ×: Cracks were generated at the folded portion of the surface of the sheet, and folding marks were also observed. △: Wrinkles, fold marks, and dents were observed on the surface of the sheet. ◯: There were no wrinkles on the surface of the sheet, but there were fold marks and dents ◎: No wrinkles, fold marks, or dents were found on the surface of the sheet (ii) Immediately after removing the weight ×: Cracks were generated at the folded portion of the surface of the sheet, and folding marks were also observed. △: Wrinkles, fold marks, and dents were observed on the surface of the sheet. ○: There were no wrinkles or fold marks on the surface of the sheet, but dents were observed. ◎: The sheet quickly returned to its original shape immediately after removal, and no wrinkles, fold marks, or dents were observed on the surface of the sheet.

[0071] <Repeated folding> A 152mm x 15mm wide sheet sample was used after the above evaluations of wrinkles, fold marks, and dents. The sheet was folded 180° and then repeatedly folded back and forth by hand 50 times. After the repeated test, the folded parts of the sheet were visually inspected and the repeated bending resistance was evaluated according to the following criteria. [Evaluation criteria] ×: The sheet was broken along the bent portion, or fraying or tearing was observed in the fiber assembly portion. △: Some fraying was observed in the fiber assembly along the bent portion. ○: No breaks, frays, or tears were observed on the exterior

[0072] Example 1 4-Methyl-1-pentene copolymer (A-1) was used in a single-screw extruder (cylinder inner diameter D: 50 mm, full-flight screw, L / D: 32 mm where L is the effective screw length, and carbon dioxide feed position: 17.5D from the screw feed side), equipped with a T-die (die width: 320 mm, lip opening: 0.5-1.8 mm), a cooling roll (outer diameter 50 mm, mirror-finished steel with hard chrome plating, water-cooled), a T-die, a cooling roll, and a take-up machine. The raw materials were melted and kneaded at a temperature of 220°C in each cylinder and a screw rotation speed of 26 rpm. The resin was extruded into a sheet form from the T-die at a resin temperature of 195°C at the cylinder head, with an extrusion rate of 4.5 kg / h. The extruded sheet was cooled with a cooling roll (water temperature inside the roll: 15°C) and taken up using a take-up machine (take-up speed: 2.3 m / min) to obtain a sheet with a width of approximately 310 mm and a thickness of 180 μm containing 4-methyl-1-pentene polymer (A-1). The resulting sheet (A-1) was placed in the center, with Y-1 ​​and Y-3 sandwiched on both sides of the sheet. A 500 μm-thick Teflon (registered trademark) sheet was placed as a release sheet, and the sheet was sandwiched between SUS plates. The sample was preheated for 3 minutes using a heat press (Toyo Seiki Seisaku-sho, Ltd., two-stage heating and cooling press) set to 160-180°C, and then pressurized at 0.5 MPa for 3 minutes to impregnate the short fiber aggregates (Y-3) and (Y-1) with the resin composition (sheet). The sample was then cooled for 3 minutes at 5 MPa using a press (Toyo Seiki Seisaku-sho, Ltd.) set to 23°C, yielding a fiber-resin composite sheet of Example 1.

[0073] <Example 2> Using a sheet containing the 4-methyl-1-pentene copolymer (A-1) produced in Example 1, Y-3 and Y-2 were placed on both sides of the sheet, and the resin composition was impregnated into Y-3 and Y-2 using the same method as in Example 1, with the heat pressing conditions being variously changed between a heating temperature of 160 to 180°C and a pressure condition of 0.5 MPa, to obtain a fiber-resin composite sheet of Example 2. At this time, when producing a sheet with a high porosity, the pressing temperature was set near the lower limit and the pressure condition was lowered.

[0074] Example 3 A sheet containing the 4-methyl-1-pentene copolymer (A-1) prepared in Example 1 was used, and Y-3 was placed on both sides of the sheet. The resin composition was impregnated into Y-3 using the same method as in Example 2, with various changes made to the conditions during heat pressing, to obtain a fiber-resin composite sheet of Example 3.

[0075] Example 4 Using 60 parts by mass of the 4-methyl-1-pentene copolymer (A-1) and 40 parts by mass of the other copolymer (B-1), a resin sheet containing the 4-methyl-1-pentene copolymer (A-1) was obtained using a T-die molding machine with a single-screw extruder similar to that in Example 1. The thickness of the sheet was 200 μm. Y-3 was placed on one side of the obtained sheet, and the resin composition was impregnated into the short fiber aggregate Y-3 using a similar method while changing the conditions during heat pressing to obtain the fiber resin composite sheet of Example 4.

[0076] <Example 5> A sheet containing the 4-methyl-1-pentene copolymer (A-1) prepared in Example 1 was used, and Y-3 and Y-1 were placed on both sides of the sheet. The resin composition was impregnated into Y-1 using the same method as in Example 2, with various changes made to the conditions during heat pressing, to obtain a fiber-resin composite sheet of Example 3.

[0077] <Comparative Example 1> The sheet of Comparative Example 1 was prepared using only the 4-methyl-1-pentene copolymer (A-1) prepared in Example 1.

[0078] <Comparative Example 2> A sheet of Comparative Example 2 was prepared using only the short fiber aggregate (Y-1).

[0079] <Comparative Example 3> A sheet containing the 4-methyl-1-pentene copolymer (A-1) prepared in Example 1 was used, and Y-4 was placed on both sides of the sheet. The resin composition was impregnated into Y-4 using the same method as in Example 1, with various changes made to the conditions during heat pressing, to obtain a fiber-resin composite sheet of Comparative Example 3.

[0080] The evaluation results of the fiber resin composites of Examples 1 to 5 and Comparative Examples 1 to 3 are shown in Table 2 below. [Table 2]

[0081] Table 2 shows that fiber-resin composite sheets obtained by impregnating short fiber aggregates with a resin composition containing a 4-methyl-1-pentene copolymer (A) that satisfies condition (A-1) have improved water repellency compared to various non-composite sheets, and the absolute value of the Δcontact angle (the difference between the contact angle immediately after and 30 seconds after) does not change significantly, and tackiness is also suppressed, confirming that the resin composition is unevenly distributed on the surface of the short fiber aggregate. It was also found that the use of an appropriate fiber aggregate with long fibers also results in excellent flexibility. [Industrial Applicability]

[0082] The fiber-resin composite of the present invention not only has excellent water repellency and tack suppression effects, but also is less likely to develop wrinkles, creases, or dents when folded, and is also less likely to break, fray, or tear with repeated folding. Therefore, the fiber-resin composite of the present invention can be used in a wide variety of applications, such as foldable daily necessities, insulated containers, and toys.

Claims

1. A fiber resin composite in which one or more sheet-like short fiber aggregates are impregnated with a resin composition, The total basis weight of the short fiber aggregate is 5 g / m ２ 80g / m or more ２ and the average fiber length of the short fibers constituting the short fiber aggregate is 2 mm or more and 30 mm or less, and The resin composition satisfies the following requirement (A-a): (A-a) the content of structural units (P) derived from 4-methyl-1-pentene is 65 mol% or more and less than 90 mol%, and the content of structural units (AQ) derived from monomers selected from the group consisting of ethylene and linear or branched α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is more than 10 mol% and 35 mol% or less; The 4-methyl-1-pentene copolymer (A) satisfies the above formula (1), and The short fibers are exposed on at least one outer surface of the fiber composite. A fiber resin composite characterized by:

2. 2. The fiber resin composite according to claim 1, wherein the structural unit (AQ) comprises a structural unit derived from a monomer selected from the group consisting of ethylene and an α-olefin having 3 to 4 carbon atoms.

3. The 4-methyl-1-pentene copolymer (A) further satisfies the following requirement (A-b): (A-b) No melting point (Tm) is observed when measured by a differential scanning calorimeter (DSC); 3. The fiber-resin composite according to claim 1 or 2, which satisfies the above.

4. The 4-methyl-1-pentene copolymer further satisfies the following requirement (A-c): (Ac) The peak temperature of the loss tangent tanδ obtained by dynamic viscoelasticity measurement in the temperature range of −40 to 150° C. at a frequency of 10 rad / s (1.6 Hz) is in the range of 15° C. or higher and 45° C. or lower, and the following requirement (Ad) is met: (Ad) the peak value of loss tangent tanδ obtained by dynamic viscoelasticity measurement in a temperature range of −40 to 150° C. and a frequency of 10 rad / s (1.6 Hz) is in the range of 1.0 or more and 5.0 or less; The fiber-resin composite according to claim 1 or 2, which satisfies the above.

5. The total basis weight of the short fiber aggregate is 5 g / m ２ 50g / m or more ２ 3. The fiber resin composite according to claim 1 or 2, wherein:

6. 3. The fiber resin composite according to claim 1, wherein the average fiber length of the short fibers constituting the short fiber aggregate is 3 mm or more and 15 mm or less.

7. 3. The fiber-resin composite according to claim 1, wherein the short fiber aggregate is a nonwoven fabric or a paper.

8. The fiber resin composite according to claim 7, wherein the short fiber aggregate is Japanese paper.

9. The fiber resin composite has a basis weight of 100 g / m ２ 250g / m or more ２ 3. The fiber resin composite according to claim 1 or 2, wherein:

10. 3. The fiber-resin composite according to claim 1, wherein the thickness of the fiber-resin composite is 40 μm or more and 300 μm or less.

11. 3. The fiber-resin composite sheet according to claim 1, wherein the fiber-resin composite has a tensile elongation at break of 5% or less.

12. A daily necessities comprising the fiber-resin composite of claim 1 or claim 2.

13. A cold storage container comprising the fiber resin composite according to claim 1 or 2.

14. A toy comprising the fiber resin composite of claim 1 or claim 2.

15. The following steps: Total basis weight is 5g / m ２ 80g / m or more ２ preparing one or more sheet-like short fiber aggregates having an average fiber length of 2 mm or more and 30 mm or less; The following requirement (A-a): (A-a) the content of structural units (P) derived from 4-methyl-1-pentene is 65 mol% or more and less than 90 mol%, and the content of structural units (AQ) derived from monomers selected from the group consisting of ethylene and linear or branched α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is more than 10 mol% and 35 mol% or less; preparing one or more sheet-shaped resin compositions containing a 4-methyl-1-pentene copolymer (A) that satisfies the above requirements; a step of overlapping the sheet-like short fiber aggregate and one sheet-like resin composition when the sheet-like short fiber aggregate is single, or sandwiching the single sheet-like resin composition between the plurality of sheet-like short fiber aggregates when the sheet-like short fiber aggregate is multiple, and hot pressing the resulting mixture; The method for producing a fiber-resin composite according to claim 1 or claim 2, comprising:

Images