JP2018095799A - Molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a molding having excellent water repellency and a good appearance.SOLUTION: A molding is molded from a resin composition containing a thermoplastic resin and silylated polyolefin, the molding having a fine rugged structure with a pitch of 20 nm to 1000 nm on its surface.SELECTED DRAWING: None

Description

  The present invention relates to a molded body having a fine uneven structure on the surface.

  In recent years, with the advancement of nanoimprint technology, there is an increasing interest in providing a water-repellent function and the like by providing a fine uneven structure on the surface of a molded body.

  For example, Patent Document 1 aims to provide a film having water repellent performance on the surface by applying surface processing without adding modifiers such as hydrophobic fine particles and a lubricant component to the film surface. It is described that a water-repellent film having a concavo-convex structure on the surface is obtained by a step of heating and melting a resin composition containing a plastic resin and a step of extruding the heat-melted resin composition onto a shaping plate and press-molding Yes.

JP 2015-24549 A

However, higher water repellency is required depending on the application. Further, according to the study by the present inventors, in the conventional thermal nanoimprint technology, the film is stretched when the thermoplastic resin film is taken out of the mold, or the transfer of the uneven shape as a whole is insufficient, or It became clear that molding defects such as uneven transfer are likely to occur.
The present invention has been made in view of the above circumstances, and provides a molded article that is excellent in water repellency and excellent in appearance and transferability of fine irregularities.

That is, this invention can be shown below.
[1]
A molded body molded from a resin composition containing a thermoplastic resin and a silylated polyolefin, wherein the molded body has a fine concavo-convex structure with a pitch of 20 nm to 1000 nm on the surface.
[2]
The molded article according to [1] above, wherein the fine uneven structure has a height of 50 nm to 10,000 nm.
[3]
The molded article according to the above [1] or [2], wherein the thermoplastic resin is polyolefin.
[4]
The molded product according to any one of [1] to [3], wherein the molded product is a film or a sheet.
[5]
The molded product according to any one of [1] to [4], wherein the total light transmittance is 90% or more.

  According to the present invention, a molded article excellent in water repellency can be provided. Moreover, the molded object of this invention has the composition excellent in the pattern transferability of the fine unevenness | corrugation shape, and is excellent in manufacturing stability. Therefore, it is possible to provide a molded article having an excellent appearance.

It is a SEM image of the film by which the fine concavo-convex structure obtained in Examples 1-2 and Comparative Examples 1-2 was transferred.

  Embodiments of the present invention will be described below with reference to the drawings. In addition, unless otherwise indicated, the symbol "ab" which shows the numerical range in a sentence shall express from a to b or less.

  The molded body of this embodiment is a molded body molded from a resin composition containing a thermoplastic resin and a silylated polyolefin, and the molded body has a fine concavo-convex structure with a pitch of 20 nm to 1000 nm on the surface. ing.

(Thermoplastic resin)
Examples of the thermoplastic resin include polyolefin, polyvinyl chloride, polyvinylidene chloride, ethylene / vinyl acetate copolymer, ethylene / methacrylic acid copolymer, polyester such as polyethylene terephthalate, polycarbonate, polyamide, ABS resin, polyacetal resin, polyimide, Examples thereof include polyurethane, polylactic acid, and the like, which can be used alone or in combination of two or more. Polyolefin is preferable as the thermoplastic resin.

  Here, the polyolefin means a polyolefin containing no silicone chain in the structural unit. Examples of the polyolefin include a polymer containing a structural unit derived from an olefin having 2 to 20 carbon atoms. Preferred polyolefins include ethylene homopolymers or copolymers and propylene homopolymers or copolymers.

  The ethylene content in the ethylene homopolymer or copolymer is preferably 50 to 100 mol%, more preferably 60 to 100 mol%. Examples of the copolymer component include α-olefins having 3 or more carbon atoms.

The MFR (ASTM D1238, 190 ° C., 2.16 kg load) of ethylene homopolymer or copolymer is preferably, for example, 0.01 to 80 g / 10 min, and more preferably 0.1 to 50 g / 10 min.
Low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene and the like are also preferable polyethylene.

As propylene homo- or copolymer, the propylene content is preferably 50 to 100 mol%. Examples of the copolymer component include ethylene and α-olefins having 4 or more carbon atoms.
The MFR (ASTM D1238, 230 ° C., 2.16 kg load) is, for example, preferably 0.1 to 100 g / 10 minutes, and more preferably 0.3 to 50 g / 10 minutes.

(Silylated polyolefin)
The silylated polyolefin may have any structure as long as it has a silicone chain and a polyolefin chain. For example, a silicone grafted polyolefin having a structure in which a silicone is grafted on a polyolefin, a block copolymer of polyolefin and silicone, a structure in which a polyolefin is grafted on silicone, a structure in which a polyolefin is grafted on the silicone part of the block copolymer, etc. Can do. One type of silylated polyolefin may be used, or two or more types may be used in combination.

Examples of the block copolymer include a block copolymer bonded in the order of (polyolefin chain)-(silicone chain), a block copolymer bonded in the order of (polyolefin chain)-(silicone chain)-(polyolefin chain), and the like. be able to.
Examples of the polyolefin chain include a polymer chain containing a structural unit derived from an olefin having 2 to 50 carbon atoms, preferably 2 to 20 carbon atoms.
Among them, those having a structure represented by the following general formula (1) are preferable.

In the above formula (1), A ¹ , A ² and A ³ are each independently a polyolefin chain or a hydrocarbon group having 1 to 20 carbon atoms. R is a hydrocarbon group having 1 to 20 carbon atoms. Each R may be the same or different. m is an integer of 1 to 10,000. When a plurality of A ³ are present, each A ³ may be the same or different. However, at least one of A ¹ , A ² , and A ³ represents a polyolefin chain.

The polyolefin chain in A ¹ , A ² and A ³ is a polymer chain including a structural unit derived from an olefin having 2 to 50 carbon atoms, preferably 2 to 20 carbon atoms, for example.

Specific examples of the olefin having 2 to 50 carbon atoms include ethylene and an α-olefin having 3 to 50 carbon atoms (propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4 -Methyl-1-pentene, 3-methyl-1-pentene, 3,4-dimethyl-1-pentene, 4-methyl-1-hexene, 3-ethyl-1-pentene, 3-ethyl-4-methyl-1 -Pentene, 3,4-dimethyl-1-hexene, 4-methyl-1-heptene, 3,4-dimethyl-1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene 1-octadecene, 1-eicocene, vinylcyclohexane, etc.).
Among these, ethylene and an α-olefin having 3 to 12 carbon atoms are preferable, ethylene and an α-olefin having 3 to 8 carbon atoms are more preferable, and ethylene is particularly preferable.
The polyolefin chain may be a homopolymer chain or a copolymer chain.

  Especially, the polymer chain comprised only from C2-C50 olefin chosen from ethylene and C3-C50 alpha olefin is preferable, Furthermore, ethylene homopolymer chain, propylene homopolymer chain, Alternatively, an ethylene / C3-C20 α-olefin copolymer chain is preferred. In the copolymer chain of ethylene / C3-C20 α-olefin, when all the structural units are 100 mol%, the structural unit derived from C3-C20 α-olefin exceeds, for example, 0 mol%. It can also be 20 mol% or less, and can also be over 0 mol% and 10 mol% or less.

  Moreover, the said polyolefin chain may also contain the structural unit derived from another olefin as needed. Other olefins include olefins containing an internal double bond such as cis-2-butene; vinylidene compounds such as isobutene; aryl vinyl compounds such as styrene; arylvinylidene compounds such as α-methylstyrene; and functionalities such as methyl methacrylate. Group-substituted vinylidene compounds; aliphatic cyclic olefins containing internal double bonds such as 5-methyl-2-norbornene, tetracyclododecene, cyclopentadiene, dicyclopentadiene; cyclic olefins containing an aromatic ring such as indene; butadiene, Examples thereof include linear or cyclic polyenes such as isoprene, ethylidene norbornene and vinyl norbornene.

  The content of structural units derived from other olefins is preferably 0 to 10 mol%, more preferably 0 to 5 mol%, assuming that all the structural units constituting the polyolefin chain are 100 mol%.

The polyolefin chain preferably has a number average molecular weight of 100 or more and 500,000 or less, more preferably 200 or more and 100,000 or less, further preferably 500 or more and 50,000 or less, and more preferably 700 or more. 10,000 or less is more preferable.
The polyolefin chain preferably has a molecular weight distribution (Mw / Mn) determined by the following GPC method in the range of 1.1 to 3.0.

GPC measurement method:
GPC measurement can be performed at a temperature of 140 ° C. using orthodichlorobenzene as a solvent, and analytical values (weight average molecular weight (Mw), number average molecular weight (Mn) and Mw / Mn) can be obtained as polyethylene conversion values. .

The measurement can be performed under the following conditions. The molecular weight can be determined based on the following conversion method by creating a calibration curve using commercially available monodisperse standard polystyrene.
Apparatus: Gel permeation chromatograph Alliance GPC2000 (manufactured by Waters)
Solvent: o-dichlorobenzene Column: TSKgel column (manufactured by Tosoh Corporation) x 4
Flow rate: 1.0 ml / min Sample: 0.15 mg / mLo-dichlorobenzene solution Temperature: 140 ° C.
Molecular weight conversion: PS conversion / general-purpose calibration method The coefficient of the Mark-Houwink viscosity equation shown below can be used for the calculation of general-purpose calibration.
Coefficient of polystyrene (PS): KPS = 1.38 × 10 ⁻⁴ , aPS = 0.70
Coefficient of polyethylene (PE): KPE = 0.06 × 10 ⁻⁴ , aPE = 0.70

In the above A ¹ , A ² , A ³ and R, examples of the hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms include an alkyl group, an arylalkyl group, an alkenyl group and an aryl group. .

Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, hexyl group, 2-ethylhexyl group, octyl group, decyl group, and octadecyl group. A linear or branched alkyl group; a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group and a norbornyl group;
Examples of the arylalkyl group include a benzyl group, a phenylethyl group, and a phenylpropyl group.
Examples of the alkenyl group include a vinyl group, a propenyl group, and a cyclohexenyl group.
Examples of the aryl group include a phenyl group, a tolyl group, a dimethylphenyl group, a trimethylphenyl group, an ethylphenyl group, a propylphenyl group, and a naphthyl group.

  In the above formula (1), m is an integer of 1 to 10,000. m is preferably 5 or more, and more preferably 10 or more. Further, m is preferably 1,000 or less, more preferably 300 or less, and even more preferably 50 or less.

All of A ¹ , A ² , and ^one or plural A ³ may be polyolefin chains, or some groups may be polyolefin chains and others may be hydrocarbon groups having 1 to 20 carbon atoms. .

In the above formula (1), m is equal to or greater than 2, when at least one of A ³ that is different from the other A ^3, but plural kinds of the following units are present, not particularly limited in its aligned sequence, block Or random.

  As said formula (1), the structure represented by following (1A), (1B) or (1C) is preferable, and (1A) is more preferable among these.

(1A) In the above formula (1), A ¹ and A ² are polyolefin chains, and A ³ is a hydrocarbon group having 1 to 20 carbon atoms.
(1B) In the above formula (1), one of A ¹ and A ² is a polyolefin chain, the other is a hydrocarbon group having 1 to 20 carbon atoms, and A ³ is a hydrocarbon group having 1 to 20 carbon atoms. There is a structure.
(1C) In the above formula (1), A ¹ and A ² are hydrocarbon groups having 1 to 20 carbon atoms, and at least one of A ³ is a polyolefin chain.

  In the silylated polyolefin according to the present embodiment, the silicone chain / polyolefin chain (weight ratio) is not particularly limited, but is preferably 5/95 to 99/1, and more preferably 10/90 to 95/5.

  The method for producing the silylated polyolefin according to the present embodiment is not particularly limited. For example, it can be produced by the method described in paragraphs 0089 to 0145 and paragraphs 0196 to 0207 of WO2012 / 098865. .

(Resin composition)
The resin composition includes a thermoplastic resin and a silylated polyolefin.
When the total of the thermoplastic resin and the silylated polyolefin is 100% by weight, the content of the silylated polyolefin is preferably 0.1 to 90% by weight, more preferably 0.1 to 50% by weight, and 3 to 30% by weight is particularly preferred. The content of the thermoplastic resin is preferably 10 to 99.9% by weight, more preferably 50 to 99.9% by weight, and particularly preferably 70 to 99.7% by weight. In addition, a molded object contains a thermoplastic resin and silylated polyolefin in said quantity.
By including the thermoplastic resin and the silylated polyolefin in the above amounts, the water repellency is more excellent.

  The resin composition may be composed of only a thermoplastic resin and a silylated polyolefin, but may further contain other resins, additives and the like as long as the object of the present invention is not impaired. Examples of additives include plasticizers, UV stabilizers, anti-coloring agents, matting agents, deodorants, flame retardants, weathering agents, antistatic agents, yarn friction reducing agents, slip agents, mold release agents, An oxidizing agent, an ion exchange agent, a coloring pigment, and the like can be added. These additives are preferably added in an amount of 1 to 20% by mass, preferably 1 to 10% by mass, based on the entire resin composition.

Each component can be melt-kneaded using a known method, for example, a single-screw or twin-screw extruder, a kneader, a Henschel mixer, a Banbury mixer, a tumbler mixer, etc., and may be used after being pelletized as necessary. it can.
Further, a master batch having a high concentration of silylated polyolefin may be prepared, and the master batch may be diluted with a thermoplastic resin.

(Fine relief structure)
From the viewpoint of the effect of the present invention, the fine uneven structure on the surface of the molded body of the present embodiment has a pitch of 20 nm to 1000 nm, preferably 30 nm to 700 nm, and more preferably 50 nm to 400 nm.

Further, the height of the fine concavo-convex structure is preferably 50 nm to 10000 nm, more preferably 50 nm to 1000 nm, and more preferably 100 nm to 500 nm from the viewpoint of the effect of the present invention.
The aspect ratio (height / pitch) can be, for example, 10 to 0.1, and preferably 5 to 0.5.

  Examples of the fine concavo-convex structure include a pillar pattern, a hole pattern, a moth-eye structure, a honeycomb structure, a lattice pattern, a line / space pattern, and other patterns, but are not limited thereto, and a desired pattern is adopted. be able to.

  Examples of the shape of the convex portion include, but are not limited to, a cone shape, a pyramid shape, an elliptical cone shape, a columnar shape, a cylindrical shape, a prismatic shape, a rectangular tube shape, a frustum, a hemisphere, a semi-ellipsoid, and a bowl shape. A desired shape can be adopted instead of the above.

The molded body having a fine uneven structure on the surface of the present embodiment is manufactured using a nanoimprint method for transferring a fine uneven transfer pattern formed on a mold to a resin composition containing a thermoplastic resin and a silylated polyolefin. Can do.
Examples of the nanoimprint method include the following methods 1 to 3.

Method 1: A method of pressing the surface of a molded body (eg, a film or the like) formed from the resin composition with a surface having a fine concavo-convex pattern of the mold.

  More specifically, a method in which a mold heated to a glass transition temperature or higher is pressure-bonded to the molded body, a method in which the molded body is heated to a glass transition temperature or higher, and the mold is pressure-bonded, or the molded body and the mold are brought to a glass transition temperature or higher. The method of heating and crimping | bonding a mold is mentioned.

  The heating temperature at the time of pressing the mold is a temperature not lower than the glass transition temperature and lower than the decomposition temperature, and is preferably (glass transition temperature + 5 ° C.) to (glass transition temperature + 30 ° C.). In the case of a crystalline resin, the heating temperature is a temperature not lower than the melting point and lower than the decomposition temperature, and is preferably a melting point + 5 ° C. to a melting point + 30 ° C. Further, the pressure bonding pressure is preferably 0.1 MPa to 50 MPa, more preferably 0.2 MPa to 20 MPa. The pressure bonding time is maintained for 10 to 600 seconds, and then the molded body from which the pattern is transferred by cooling is separated from the mold. The temperature at the time of separation is preferably a temperature not higher than the glass transition temperature, and more preferably not higher than (glass transition temperature −30 ° C.). In the case of a crystalline resin, the temperature at the time of separation is preferably at a temperature below the melting point, preferably at a temperature below the melting point −30 ° C.

Method 2: A method in which the resin composition is heated and melted, and the heat-melted resin composition is extruded onto a surface having a fine concavo-convex pattern of the mold, followed by pressure molding.

The temperature at which the resin composition is heated and melted is preferably 100 to 400 ° C, more preferably 120 to 350 ° C, and still more preferably 150 to 300 ° C.
The mold is preferably provided with a temperature control device such as a heating device or a cooling device. The temperature of the shaping plate is preferably 50 to 300 ° C, more preferably 60 to 270 ° C, and still more preferably 70 to 250 ° C.

As the mold, a roll or flat mold can be used.
As an example, a film can be formed by pressurizing the heated and melted tree composition extruded from a T die when the surface is passed between a chill roll and a nip roll whose surface has been processed with fine irregularities. . In this embodiment, a chill roll is used as a roll-shaped mold.
As another example, a film can also be formed by pressing a resin pellet made of the resin composition with a flat plate mold having a concavo-convex structure on the surface while heating.

Method 3: A method in which the solution or dispersion containing the resin composition is dried after contacting the surface of the mold having the fine concavo-convex pattern.
The resin composition is dissolved in a dissolvable or dispersible medium to prepare a solution or dispersion. There is no restriction | limiting in particular in the density | concentration of the resin composition in a solution or a dispersion liquid.
The solution or dispersion may be applied to the mold, or after being applied to the substrate or the like, the mold may be contacted.

Examples of the coating method include spin coating, dipping, spray coating, dispensing, ink jet, roll to roll, gravure, die coating, bar coating, and curtain coating.
The drying temperature and time can be appropriately set in consideration of the boiling point and volatility of the medium.

(Molded body)
The molded body of the present embodiment may have any shape as long as the surface has the fine concavo-convex structure described above, but is preferably a film or a sheet.

  The molded body of this embodiment is formed by molding the resin composition by a known method such as an extrusion molding method, an injection molding method, a melt casting method, an inflation molding method, a compression molding method, a transfer molding method, or a casting molding method. be able to.

Further, the molded body of the present embodiment may be a laminate.
As a manufacturing method of a laminated body, for example,
1) A method of bonding a layer having a fine concavo-convex structure formed from the resin composition and another layer so that the surface has a fine concavo-convex structure,
2) After obtaining a laminate of the resin composition layer and other layers by a known method such as coextrusion molding or bonding, fine irregularities are transferred to the surface of the resin composition layer. Method,
Etc.

The other layer may be one layer or two or more layers. Further, the materials constituting the other layers can be appropriately selected from various materials such as resin, metal, paper, and cloth depending on the application.
The molded body of this embodiment is excellent in water repellency and in appearance. Furthermore, the transparency of the molded body may be improved.

  For example, on the surface of a film formed from a resin composition containing polyolefin and silylated polyolefin, external haze occurs due to irregular reflection of light due to crystals or random unevenness, but a fine uneven shape (preferably moth-eye structure; preferably 400 nm or less This can be eliminated by improving the transparency. Although the total light transmittance of the obtained molded body is not particularly limited, it can be, for example, 90% or more when used for applications requiring transparency.

(Use)
Examples of uses of the molded body of the present embodiment include the following, but are not limited thereto.

  Water-repellent film, oil-repellent film, packaging materials; mainly anti-reflection films, protective films, reflective polarizing films for mobile phones, smartphones, tablets, touch panels, solar cells, LEDs, etc .; Panel light extraction film; Light guide plate; Antibacterial sheet; Cell culture material; Virus detection sensor material; LED brightness enhancement; Anti-transparent micromirror

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, the scope of the present invention is not limited to these Examples.

[Synthesis Example 1]
According to the method described in Synthesis Example 2 of International Publication No. 2012/098865, a one-end vinyl group-containing ethylene polymer (P-1) was synthesized. The physical properties of this one-end vinyl group-containing ethylene polymer (P-1) (single unit) were as follows.
Melting point (Tm) 127 ° C. (DSC)
Mw = 4800, Mw / Mn = 2.3 (GPC)
Terminal unsaturation 97%

[Synthesis Example 2]
A 300 ml two-necked flask was charged with 25.1 g (11.8 mmol) of the one-end vinyl group-containing ethylene polymer (P-1) obtained in [Synthesis Example 1], and the following structure was obtained under a nitrogen atmosphere. 6.2 g (5.9 mmol; equivalent to 11.8 mmol as Si—H group) of hydrosilane A (Gelest, Inc., DMS-H11) and platinum prepared according to Synthesis Example 3 of International Publication No. 2012/098865 150 μl of the catalyst composition (C-1) diluted 200-fold with hydrosilane A (1.4 × 10 ⁻⁶ mmol in terms of Pt) was charged. The reactor was set in an oil bath that had been heated to an internal temperature of 130 ° C. in advance, and stirred. The mixture was stirred in an oil bath for 6 hours and then cooled, about 200 ml of methanol was added, and the contents were taken out into a 300 ml beaker and stirred for 2 hours. Thereafter, the solid is collected by filtration and dried, whereby in formula (1), A ¹ and A ² are ethylene homopolymer chains, A ³ is a methyl group, R is a methyl group, and m is 12 33.5 g of a white solid silylated polyolefin of ˜13 was obtained. As a result of NMR analysis, the obtained silylated polyolefin had a yield of 99%, an olefin conversion rate of 100%, and an isomerization rate of 1%. The number average molecular weight analyzed by GPC was 5,000.
Hydrosilane _{A: HSi (CH 3) 2} O - (- Si (CH 3) 2 -O-) n -Si (CH 3) 2 H (n = 12~13)

[Example 1]
(Creation of two-layer film)
90 parts by mass of low density polyethylene (Mitsui DuPont Polychemical, Mirason 12P) and 10 parts by mass of silylated polyolefin obtained in Synthesis Example 2 were put into a TEM-26SS twin screw extruder (L / D = 60) manufactured by Toshiba Machine. The mixture was melt-mixed at a cylinder temperature of 200 ° C. to obtain a resin composition (C1). Resin composition (C1) layer obtained at a surface temperature of 5 μm at a T die temperature of 200 ° C. using a three-type three-layer film forming apparatus manufactured by Thermo Plastics Co., Ltd. A two-layer film having a layer film made by Polychemical Co., Ltd., Mirason 12P) was formed. The thickness was 50 μm.

The contact angle of this two-layer film and pure water was measured using a contact angle measuring device (manufactured by Kyowa Interface Science Co., Ltd., solid surface energy analyzer CA-XE type) and found to be 101 °.
Moreover, when the total light transmittance and haze of this two-layer film were measured using a haze meter TC-HIIIDPK manufactured by Tokyo Denshoku Co., Ltd., the total light transmittance was 89.6%, and the haze was 17.7%. there were.

(Nanoimprint)
For nanoimprinting by thermocompression bonding, a small thermal imprinting device manufactured by Toray Engineering Co., Ltd. was used.
The two-layer film was heated to 140 ° C., the fine concavo-convex pattern surface of the mold was brought into contact with the C1 layer, and thermocompression bonded at 5 MPa and held for 30 seconds. After cooling to 40 ° C., the film was taken out of the mold, and a film having a thickness of 50 μm with fine irregularities transferred to the C1 layer was obtained. As the mold, a mold having a moth-eye structure with an average height of 250 nm and a pitch of 250 nm was used on the surface. The obtained uneven transfer film had good appearance and good pattern transferability. The SEM image is shown in FIG.
Further, the contact angle of pure water of the uneven transfer film was measured by using a contact angle measuring device (manufactured by Kyowa Interface Science Co., Ltd., solid surface energy analyzer CA-XE type) and found to be 124 °.
Moreover, when the total light transmittance and haze of the uneven transfer film were measured using a haze meter TC-HIIIDPK manufactured by Tokyo Denshoku Co., Ltd., the total light transmittance was 92.9% and the haze was 2.7%. It was.

[Comparative Example 1]
An uneven transfer film was obtained in the same manner as in Example 1 except that the silylated polyolefin was not used. The obtained concavo-convex transfer film was stretched when taken out from the mold, and the appearance was poor. The SEM image is shown in FIG.
Moreover, the obtained uneven | corrugated transfer film was inferior to shaping | molding, the surface was not uniform, and the variation in the water contact angle was large.

[Example 2]
(Creation of two-layer film)
90 parts by mass of polypropylene (polypropylene manufactured by Prime Polymer Co., Ltd., F300SP) and 10 parts by mass of silylated polyolefin obtained in Synthesis Example 2 were cylinder temperature 230 using a TEM-26SS twin screw extruder (L / D = 60) manufactured by Toshiba Machine Co., Ltd. It melt-mixed at 0 degreeC and obtained the resin composition (C2). The resin composition (C2) layer obtained on a surface layer of 5 μm at a T-die temperature of 230 ° C. using a three-layer three-layer film forming apparatus manufactured by Thermo Plastics Co., Ltd. Polypropylene (manufactured by Prime Polymer Co., Ltd.) A two-layer film having a polypropylene, F300SP) layer film was molded. The thickness is 50 μm.
When the contact angle between this two-layer press film and pure water was measured in the same manner as in Example 1, it was 103 °.

(Nanoimprint)
For nanoimprinting by thermocompression bonding, a small thermal imprinting device manufactured by Toray Engineering Co., Ltd. was used. The two-layer film was heated to 180 ° C., the fine concavo-convex pattern surface of the mold was brought into contact with the C2 layer, thermocompression bonded at 5 MPa, and held as it was for 30 seconds. After cooling to 40 ° C., the film was taken out of the mold to obtain a film having a thickness of 50 μm with fine irregularities transferred to the C2 layer. As the mold, a mold having a moth-eye structure with an average height of 250 nm and a pitch of 250 nm was used on the surface. The obtained uneven transfer film had good appearance and good pattern transferability. The SEM image is shown in FIG.
Moreover, when the contact angle of the uneven | corrugated transfer film and pure water was measured similarly to Example 1, it was 130 degrees. Moreover, when the total light transmittance of the uneven | corrugated transfer film was measured similarly to Example 1, it was 93.0%.

[Comparative Example 2]
An uneven transfer film was obtained in the same manner as in Example 2 except that the silylated polyolefin was not used. The obtained uneven transfer film had uneven transfer of fine unevenness, and overall transfer was insufficient. The SEM image is shown in FIG.
Moreover, the obtained uneven | corrugated transfer film was inferior to shaping | molding, the surface was not uniform, and the variation in the water contact angle was large.

Claims (5)

  A molded body molded from a resin composition containing a thermoplastic resin and a silylated polyolefin, wherein the molded body has a fine concavo-convex structure with a pitch of 20 nm to 1000 nm on the surface.   The shaped body according to claim 1, wherein the height of the fine concavo-convex structure is 50 nm to 10000 nm.   The molded article according to claim 1 or 2, wherein the thermoplastic resin is a polyolefin.   The molded object in any one of Claims 1-3 whose molded object is a film or a sheet | seat.   The molded article according to any one of claims 1 to 4, having a total light transmittance of 90% or more.