JP2005054118A - Non-adherent multiple surface structure - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a surface structure with which adhesion itself of various adherent materials can be controlled, the materials being not concerned with their natures, shapes, size, etc. <P>SOLUTION: The multiple surface structure comprises (1) including two kinds of primary surface units A and B whose contact angles for water are different, and the difference of the contact angles for water being maximum, (2) making the primary surface unit A to include a secondary surface unit α having the contact angle for water different from the primary surface unit A, and/or making the primary surface unit B to include a secondary surface unit β having the contact angle for water different from the primary surface unit B, and (3) including adjacent primary surface units having different contact angles for water. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a surface structure having a multi-layer structure in which various contaminants and substances are basically difficult to adhere regardless of hydrophobicity and hydrophilicity.

  According to the present invention, a non-adhesive surface can be provided regardless of the nature and size of the adhesive substance, and a non-adhesive surface can be provided to various articles that are difficult to clean. , Leading to significant cost savings, including maintenance.

  The current situation in antifouling technology is known as a method for making the surface highly hydrophobic (water and oil repellency), a method for making the surface highly hydrophilic, and a method for blending a photocatalyst.

  The method of hydrophobizing the surface is a method of repelling water and oil by increasing the energy of the surface and making it easier to remove the attached dirt, but it is defenseless against adhesion of dirt due to static electricity, and adhesion It cannot prevent itself.

  In addition, the method of hydrophilizing the surface is to reduce the surface energy, making it difficult to attach hydrophilic dirt as well as hydrophobic dirt. However, fine dirt such as cigarette smoke and oily smoke is attached. It is not so effective in preventing

  Further, the method of blending the photocatalyst is a method of oxidizing and decomposing dirt adhering to the surface by the action of the photocatalyst. However, it is expensive and there are restrictions on the choice of the material to be a matrix, and there are restrictions in use.

  Therefore, it has been proposed to adopt a surface structure of a microphase separation structure based on the research results of biological membranes. A microphase-separated structure is a structure in which a hydrophilic phase and a hydrophobic phase are finely distributed. In some situations, the hydrophilic phase performs its function, and in other situations, the hydrophobic phase performs its function. is there.

  For example, Patent Document 1 is known in the field of medical materials such as artificial blood vessels and medical instruments. Also, Patent Document 2 is known in the marine paint field such as ship bottom paint. Further, Patent Documents 3 and 4 are known in the field of electrical products. Further, Patent Documents 5 and 6 are known in the fields of water droplet adhesion prevention and snow accretion prevention.

JP-A-6-14989 Japanese Patent No. 1368280 Japanese Patent Laid-Open No. 2003-160681 JP 2003-161460 A JP-A-4-285199 JP 7-166123 A

  However, none of the literature has achieved a phase separation structure that is uniform, fine, and excellent in mechanical strength (durability), so that the microphase separation structure formed can cope with all stains.

  For example, in the medical material field such as Patent Document 1, for the purpose of antithrombotic action, the target adherent substance is limited to biological substances such as platelets, and optimization thereof is being studied, and the surface hardness is so much. It is not high and the microphase separation structure is insufficient, so it is inferior in anti-adhesion ability and durability in the field of anti-adhesion in general-purpose articles such as outdoor articles exposed to a wide variety of air pollutants. Have the following issues.

  In the marine paint field such as Patent Document 2, it is specialized in preventing the adhesion of marine organisms, and only a simple phase separation structure has been achieved, and outdoor articles exposed to a wide variety of airborne contaminants. In the field of adhesion prevention in general-purpose articles, there are problems such as poor adhesion prevention ability.

  In Patent Documents 3 and 4, a commercially available acrylic clear paint (coating composition composed of acrylic resin, alkoxysilane, and colloidal silica) is applied to develop a microphase separation structure. Needs to be improved in terms of heterogeneity, mechanical strength, and compactness.

  Further, in Patent Document 5, a water-repellent film is partially formed on a hydrophilic metal substrate, but water landing or snow accretion occurs at the metal portion. Further, Patent Document 6 proposes to use a water-repellent resin as a base material instead of a metal base material. However, since it is easy to be charged, there is a problem that adhesion of a charged substance proceeds.

  As described above, there is a limit to uniformly dealing with dirt and substances having different properties, shapes, and sizes by simply distributing the hydrophilic phase and the hydrophobic phase.

  In general, hydrophobic substances (surfaces with a large water contact angle) are likely to adhere to hydrophobic substances (contaminants, etc.), and hydrophilic surfaces (surfaces with a small water contact angle) are likely to adhere to hydrophilic substances (contamination). It is known that substances etc. are likely to adhere.

  In addition, as shown in FIG. 2, the mechanism for adhering substances (contaminants etc.) to adhere to the surface includes, for example, single adhesion of a large adhering substance 12 to the surface unit 10 and small adhering substance to the surface unit 11. It is believed that there are 13 multilayer deposits (adhesion layer growth).

  Therefore, for example, if the size (width) of the surface unit 10 is reduced, the interface in contact with the large adhesive substance 12 is reduced, and distortion 14 occurs due to the influence of the adjacent surface 11 with different water contact angles, and adhesion is unlikely to occur. It is estimated that In addition, if the size (width) of the surface unit 11 is reduced, the number of small adhesive substances that accumulate is reduced, and it is presumed that the adhesion of the substances is suppressed.

  In this way, a method of suppressing the adhesion of the adhesive substance by controlling (particularly small) the size (width) of the surface units 10 and 11 themselves is conceivable. However, the method of controlling (reducing) the surface units 10 and 11 itself requires precise control for adjusting the width.

  As a means for suppressing the adhesion of adhesive substances, the present inventors have studied to obtain the same effect while leaving the surface units 10 and 11 themselves as they are. As a result, for example, the surfaces of the surface units 10 and 11 are finely divided. Thus, the inventors have found that by providing fine surface units having different contact angles with water, the surface adhesion can be suppressed regardless of the nature, size, and shape of the adhesive substance, and the present invention has been completed.

That is, the present invention relates to a non-adhesive multiple surface structure having the following multiple surface structure.
(1) including two types of primary surface units A and B having different water contact angles and a difference in water contact angle of 20 degrees or more,
(2) The primary surface unit A has a secondary surface unit α having a water contact angle different from that of the primary surface unit A in its surface structure, and / or the primary surface unit B is different from the primary surface unit B Including a secondary surface unit β having a contact angle with water in its surface structure,
(3) Adjacent primary surface units have different water contact angles.

  The contact angle with water is measured by a 1 / 2θ method using a CA-A contact angle meter manufactured by Kyowa Denshi Kagaku Co., Ltd.

  In the multiple surface structure of the present invention, the primary surface unit A is a surface having a large water contact angle (hydrophobic surface) and the primary surface unit B is a surface having a small water contact angle (hydrophilic surface) schematically. If it represents, it will become like FIG.

  The multiple surface structure of the present invention includes a primary surface unit 1 (surface unit A) having a large water contact angle and a primary surface unit 2 (surface unit B) having a small water contact angle. One or a plurality of secondary surface units 3 (surface unit α) having a smaller water contact angle than the surface unit A are formed in the primary surface unit 1, and the surface unit 1 is further finely divided. One or a plurality of secondary surface units 4 (surface units β) having a larger water contact angle than the surface unit B are formed in the primary surface unit 2, and the surface unit 2 is further finely divided.

  The multiple surface structure may be further multiplexed, and at least one of the m-th order surface units (m is an integer of 2 or more) may further include m + 1-order surface units having different water contact angles.

  By dividing each surface unit into multiple layers in this way, the large hydrophobic adhesive substance 5 which is to adhere to the hydrophobic primary surface unit 1 is caused by the presence of the secondary surface unit 3 at the interface with the primary surface unit 1. Strain is generated and adhesion is weakened, and adhesion is further suppressed. Further, the small hydrophilic adhesive substance 6 which is intended to adhere to the hydrophilic primary surface unit 2 has the primary surface unit 2 as the secondary surface unit 4. Therefore, it is considered that the number of adherent substances adhering to the finely divided surface of the primary surface unit 2 is limited, and as a result, the number of adherent substances that accumulate is greatly reduced. The behavior of the small hydrophobic adhesive substance 7 with respect to the hydrophobic primary surface unit 1 is similar.

  When the multi-surface structure of the present invention is adopted, it is possible to suppress the adhesion itself of a wide variety of adhesive substances regardless of the nature, shape, size, etc. of the adhesive substances.

  The multi-surface structure of the present invention includes two types of primary surface units A and B having different water contact angles and a difference of 20 ° or more in the water contact angle. Of course, other surface units C having an intermediate water contact angle between the primary surface units A and B may be included. Even in that case, adjacent primary surface units need to have different water contact angles. As described above, the other surface unit C is preferably selected in consideration of this point, since it is preferable that the difference in the contact angle with water between adjacent surface units is large in order to effectively inhibit adhesion. .

Examples of the arrangement of primary surface units include the following.
(1) -A-B-A-B-
(2) -ABC-
(3) -A-C-B-
(4) -A-C-B-C-

  The difference between the primary surface units A and B with respect to the water contact angle is 20 degrees or more, and is preferably the largest among the primary surface units forming the surface (secondary surface units are not considered), and the difference is large. Is preferred. Specifically, it is preferably 30 degrees or more, and more preferably 40 degrees or more. The upper limit of the difference is theoretically 180 degrees.

  From another viewpoint, when the primary surface unit is formed of an organic substance (for example, resin), the difference in SP (solubility power) between the primary surface units A and B is 1 or more, and the primary surface forms the surface. The largest unit is desirable (secondary surface units are not considered), and the difference is preferably larger. Specifically, it is preferably 2 or more, more preferably 3 or more.

  The other surface unit C is formed when another characteristic is imparted to the surface. Another surface property includes photocatalytic properties.

  The multiple surface structure of the present invention is that the primary surface unit further includes a secondary surface unit. Of course, as long as the relationship between the surface units A and α and the surface units B and β is maintained, they may be multiplexed (n-fold) as much as possible. Hereinafter, in order to make the explanation easy to understand, the double surface structure (n = 2) is used as a representative example, and the primary surface unit A is a (hydrophobic) surface unit having a large water contact angle, as in the description of FIG. The primary surface unit B will be described as a (hydrophilic) surface unit having a small contact angle with water, but the reverse is also true.

  The multi-surface structure of the present invention includes a primary surface unit A including a secondary surface unit α having a smaller water contact angle than the primary surface unit A, and / or a secondary surface unit having a larger water contact angle than the primary surface unit B. Primary surface unit B including β is included.

  The secondary surface unit α formed on the primary surface unit A is only required to have a smaller water contact angle than the surface unit A. From the viewpoint of preventing the adhesion of the hydrophobic adhesive substance, the difference in the water contact angle is different. Is preferably larger. However, it is not necessary to relate the water contact angle of the secondary surface unit α to the water contact angle of the primary surface unit B, and the water contact angle of the secondary surface unit α is larger than that of the primary surface unit B. Can be large, the same or small.

  Similarly, the secondary surface unit β formed on the primary surface unit B is only required to have a larger water contact angle than the surface unit B. From the viewpoint of preventing adhesion of the hydrophilic adhesive substance, the surface contact with water A larger angle difference is preferred. However, there is no need to relate the water contact angle of the secondary surface unit β to the water contact angle of the primary surface unit A, and the water contact angle of the secondary surface unit β compared to the primary surface unit A. May be small, the same, or large.

  The method for forming the multi-surface structure of the present invention will be described later. In particular, when one of the primary surface units A or B is a crystalline part and the other is an amorphous part, This is desirable in terms of suppressing adhesion and further growth of the crystal.

  In general, an adhesive substance has a property that materials having the same or similar properties gather together, and as a result, often has a crystal or crystal-like structure. In such a case, it is necessary to arrange regularly in order for the crystal of the adhesive substance to grow, and for this reason, it is preferable that the property of the adhesion surface is the same. However, when the surface is subdivided into a crystalline surface and an amorphous surface, it is difficult to regularly arrange and grow the adherent material, and as a result, the crystal growth and sticking of the adherent material is suppressed. It is estimated that Which surface unit is to be crystallized may be determined by selecting a material.

  As the crystalline adhesive substance, oily smoke (a single molecule of oil), wax, fuel oil, various scales, various sludges, various salts (such as sodium chloride), and water (ice) are well known. is there.

  A feature of the present invention is that a secondary surface unit is provided in the primary surface unit. The secondary surface unit plays a role of inhibiting the adhesion of substances adhering to the primary surface unit by providing minute regions with different water contact angles in the primary surface unit. From this viewpoint, the average maximum width of the secondary surface unit is preferably 2 nm or more, and more preferably 5 nm or more. If the average maximum width is too small, it becomes difficult to form surface units, and as a result, the contact area with a large adhesive substance becomes absolutely large and the distortion effect becomes dilute, making it difficult to suppress adhesion. The upper limit is preferably 5 μm, more preferably 1 μm, particularly 200 nm, especially 50 nm. If it is too wide, the significance of finely dividing the secondary surface unit is lost.

  In the present invention, the maximum width of the primary surface unit is not fixedly determined in relation to the size of the target adhesive substance, but is an important factor. If the maximum width is too large, the contact area of a large adhesive substance becomes absolutely large even if it is finely divided in units of secondary surfaces, making it difficult to suppress adhesion. The average maximum width of the primary surface unit is preferably 20 times or less, more preferably 10 times or less, and particularly preferably 5 times or less of the average maximum width of the secondary surface unit in relation to the secondary surface unit. If it is too wide, there may be a problem that even if it is finely divided in units of secondary surface, the contact area of a large adhesive substance becomes absolutely large and it becomes difficult to suppress the adhesion. The lower limit is preferably about twice the average maximum width of the secondary surface units. Below that, the purpose of forming the secondary surface unit is not achieved (the same as the case of only the primary surface unit).

  There is a suitable average maximum width due to the difference in use environment, that is, the type and combination of adhesive substances. These will be described later.

  In addition, it is preferable that the average maximum width of one primary surface unit is the same as the average maximum width of the other primary surface unit, that is, 1 or less, from the viewpoint of effective influence of distortion on the adhesive substance. The lower limit is preferably 1/10 or more, and more preferably 1/5 or more, from the viewpoint that adhesion of a wide range of adhesive substances can be prevented.

  The primary surface unit and the secondary surface unit have various shapes such as a circle, a polygon, and an indefinite shape in plan depending on the forming method. Therefore, in the present invention, the maximum width of the primary and secondary surface units refers to the maximum distance to which the adhesive substance can adhere. This maximum width can be measured by the following method.

(Measurement method of maximum width of surface unit)
When the surface unit is relatively large, it can be measured by coating the sample with a conductive material and then observing it with a scanning electron microscope (SEM). Further, when the surface unit is smaller, it can be measured by coating the sample with osmium by a plasma CVD apparatus and then observing it with an SEM. Alternatively, it can be measured by observing with a field emission (FE) apparatus.

  Further, in order to more effectively inhibit the adhesion of various adhesive substances having different properties, shapes, and sizes, it is desirable to reduce the variation in the maximum width of the same type of surface unit. From this viewpoint, 50% or more of the maximum width of each primary surface unit and secondary surface unit, more preferably 80% or more, particularly 90% or more is in the range of 1/3 to 3 times the average maximum width, or 1 It is preferably in the range of 2-2 times.

  Regarding the relationship between the shape and dispersion of the hydrophilic surface and the hydrophobic surface in the multiple surface structure of the present invention, one is the sea (matrix) and the other is the island-island structure, and the columnar structure is dispersed in the matrix in the form of columns. There are an OBDD structure which is an intermediate structure between a columnar structure and a lamellar structure, a lamella structure in which crystal regions are finely dispersed, and the like, but the structure is not limited to these structures.

  The material for forming the primary surface unit and the secondary surface unit in the present invention will be described together in the following description of the method for forming a multiple surface structure.

  The multi-surface structure of the present invention can be formed by the following method.

(Formation method 1)
(I) a high molecular weight block copolymer or graft copolymer comprising a segment for forming primary surface unit A and a segment for forming primary surface unit B; (II) a segment for forming secondary surface unit α and primary surface unit A; Low molecular weight block copolymer or graft copolymer containing a segment having affinity and / or low molecular weight block copolymer containing a segment having an affinity for secondary surface unit β-forming segment and primary surface unit B A method for forming a multi-surface structure in which a composition obtained by mixing a coalescence or a graft copolymer is applied or molded.

  In this formation method 1, a primary surface unit is formed by a high molecular weight block copolymer or graft copolymer (hereinafter, described as being representative of a block copolymer unless otherwise specified) (I). That is, the polymer chain of the high molecular weight block copolymer itself includes a hydrophobic segment that forms a hydrophobic primary surface unit A and a hydrophilic segment that forms a hydrophilic primary surface unit B. Surface) -island (hydrophilic surface) structure is formed. It should be noted that the surface properties of the surface units A and B may be reversed.

  Each segment may be crystalline or amorphous, and one or both may be crystalline or amorphous.

  Examples of the crystalline segment include, but are not limited to, an olefin segment such as ethylene and propylene; a fluorinated olefin segment; an ethylene glycol segment; a polyamide segment; and a vinyl chloride segment. Examples of the amorphous segment include, but are not limited to, an aromatic vinyl segment such as styrene and vinyltoluene, a glycidyl methacrylate segment, and a styrene sulfonic acid segment.

  The segment ratio A / B between the primary surface unit A forming segment and the primary surface unit B forming segment in the copolymer (I) is 1/20 or more, more preferably 1/10 or more, particularly 1/5 or more. In view of the balance between the hydrophobic surface and the hydrophilic surface, it is preferably 1/1 or less, more preferably 3/4 or less.

The low molecular weight block copolymer (II) is
(IIα) a low molecular weight block copolymer comprising a segment for forming secondary surface unit α and a segment having affinity for primary surface unit A,
(IIβ) It is at least one of a low molecular weight block copolymer comprising a segment for forming secondary surface unit β and a segment having affinity for primary surface unit B. In order to form a highly finely divided multi-surface structure, it is preferable to blend both copolymers (IIα) and (IIβ).

  In these low molecular weight block copolymers, in the copolymer (IIα), the surface unit A affinity segment is compatible with the surface unit A to fix the block copolymer (IIα) in the surface unit A. The segment for forming the surface unit α forms the secondary surface unit α in the surface unit A to form a multiple surface structure. In the copolymer (IIα), the ratio (weight ratio) between the segment for forming secondary surface unit α, the primary surface unit A and the affinity segment is 1/20 or more, further 1/10 or more, particularly 1/5. It is above, and it is preferable that it is 1/1 or less, and further 3/4 or less from the viewpoint that fine division of the hydrophobic surface or the hydrophilic surface is appropriately expressed. These conditions are the same for the copolymer (IIβ).

  Since the block copolymer for forming the secondary surface unit has a low molecular weight, it can move relatively freely and easily bleed out to the surface region, so that a multiple surface structure can be easily formed on the target surface unit.

  The weight average molecular weight of the high molecular weight copolymer (I) is preferably 1,000 or more, more preferably 2,500 or more, and particularly preferably 10,000 or more, from the viewpoint of providing necessary coating strength, and 1,000,000. Hereinafter, further, 100,000 or less, particularly 50,000 or less is preferable from the viewpoint of securing appropriate processability (formability and coating property).

  The weight average molecular weight of the low molecular weight copolymer (II) is 1/2 or less, more preferably 1/5 or less that of the high molecular weight copolymer (I). This is preferable because a secondary surface structure can be easily formed in the primary surface structure. If the molecular weight is too small, the surface completely bleeds out and a durable multiple surface structure cannot be obtained.

  The weight average molecular weight in the present invention is measured by gel permeation chromatography (GPC) and converted to polystyrene.

  As the copolymer for forming the primary surface unit, a known block copolymer or graft copolymer can be used, for example, a polystyrene-polyhydroxylalkyl (meth) acrylate block copolymer, a polymethyl (meth) acrylate-polyhydroxylalkyl. Block copolymers such as (meth) acrylate block copolymers, polypropylene-maleic anhydride copolymers, styrene-maleic anhydride block copolymers, styrene-maleimide block copolymers; styrene- (meth) acrylic acid grafts Examples thereof include, but are not limited to, a graft copolymer such as a copolymer. Commercially available hydrophilic segment-hydrophobic segment block copolymers and graft copolymers can also be used.

  As the copolymer for forming the secondary surface unit, a nonionic surfactant can be used in addition to the low molecular weight material of the copolymer for forming the primary surface unit. Nonionic surfactants include, for example, polyoxyethylene (n = 10) octylphenyl ether, polyoxyethylene (n = 23) lauryl ether, polyoxyethylene (n = 20) sorbidan monolaurate, polyoxyethylene (N = 20) Polyoxyethylene type nonionic surfactant such as sorbidan paramitate; polyether modified silicone type cost ionic surfactant (for example, SH3747, SH3771, SH8400, SH8700, SF8419. As a preferred example, a product name, manufactured by Co., Ltd.

  The mixing ratio of the high molecular weight copolymer (I) and the low molecular weight copolymer (II) may be appropriately selected depending on the combination and the like. For example, the copolymer (II) is added to 100 parts by weight of the copolymer (I). 1 part by weight or more, further 5 parts by weight or more, particularly 20 parts by weight or more, 200 parts by weight or less, more preferably 100 parts by weight or less, and particularly preferably 50 parts by weight or less.

  The mixing method differs depending on whether it is a paint form or a molding material.

  When preparing a solvent-type paint among the paint forms, in addition to a solvent capable of dissolving or dispersing the high molecular weight copolymer (I) and the low molecular weight copolymer (II), the multi-surface structure of the present invention is destroyed. As long as it is not, the usual additives may be blended and stirred and mixed.

  Examples of the solvent include ketones, esters, ester ethers, hydrocarbons, amides, alcohols, or mixed solvent systems thereof.

  Specifically, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ester solvents such as ethyl acetate, n-butyl acetate and isobutyl acetate; ester ether solvents such as cellosolve acetate; toluene, xylene and the like Hydrocarbon solvents; amide solvents such as dimethylformamide; alcohol solvents such as methanol, methanol, isopropanol, n-ethanol, isobutanol and cyclohexanol.

  In the case of preparing a powder coating material, if both of the copolymers (I) and (II) are solid, they may be dry blended and powdered by a conventional method. When the low molecular weight copolymer (II) is in a liquid state, it may be impregnated into an appropriate porous powder to form a powder coating.

  When preparing an aqueous dispersion type paint, a usual method such as mixing aqueous dispersions of particles of the copolymers (I) and (II) is employed.

  Examples of the additive include pigments, dyes, fillers, antioxidants, leveling agents, reinforcing fibers, ultraviolet absorbers, photocatalysts, and light stabilizers.

  The coating method is not particularly limited, and may be any method that can form a uniform coating such as a brush coating method, a spray method, a dipping method, a roll coating method, or an electrostatic coating method.

  As the treatment after painting, a drying treatment including natural drying, a crystallization promotion treatment, and the like can be appropriately performed as necessary.

  The thickness of the coating film is not particularly limited, but is preferably 100 nm or more, more preferably 500 nm or more, and particularly preferably 5 μm or more from the viewpoint that the coating film strength and an appropriate multiphase separation structure can be formed. The upper limit is not particularly limited as long as the coating film does not crack or crack.

  When preparing a molding material, if high molecular weight copolymer (I) and low molecular weight copolymer (II) are required, add additives, then dry or wet mix, melt melt knead and pelletize The method to do is common.

  As the molding method, a general molding method such as a melt extrusion molding method or an injection molding method can be employed without any particular limitation.

  Examples of the shape of the molded product include shapes of various products in addition to films, sheets, and boards.

(Formation method 2)
(Ia) a block copolymer or graft copolymer comprising a primary surface unit A-forming segment and a secondary surface unit α-forming segment; (Ib) a primary surface unit B-forming segment and a secondary surface unit β-forming segment; A method for forming a multi-surface structure in which a composition containing a block copolymer obtained by copolymerizing a block copolymer or a graft copolymer containing is coated or molded.

  In this formation method, a block copolymer capable of forming a multiple surface structure is produced by further block copolymerizing two or more types of block copolymers in which secondary surface units are previously incorporated into primary surface units. It is a method for forming a multiple surface structure by coating or molding using a block copolymer.

  Therefore, the block copolymer (Ia) usable in this method is a block copolymer obtained by block copolymerization of the primary surface unit A-forming segment and the secondary surface unit α-forming segment described in the formation method 1. The block copolymer (Ib) is a block copolymer obtained by block copolymerization of the primary surface unit B forming segment and the secondary surface unit β forming segment described in the formation method 1, The above-mentioned specific examples can be illustrated for any segment.

  The ratio of the primary surface unit A forming segment to the secondary surface unit α forming segment in the copolymer (Ia) is 1/1 or more, more preferably 4/3 or more, and 20/1 or less in terms of weight ratio. Further, 10/1 or less, particularly 5/1 or less, is that the balance between the hydrophobic surface unit and the hydrophilic surface unit is good, especially the hydrophilic secondary surface unit α in the hydrophobic primary surface unit A. Is preferable in that it is appropriately dispersed. The same ratio is preferable in the copolymer (Ib).

  The copolymerization ratio (Ia) / (Ib) of the copolymers (Ia) and (Ib) is 1/20 or more, more preferably 1/10 or more, particularly 1/5 or more in weight ratio, 20/1 or less, Further, 10/1 or less, particularly 5/1 or less is preferable from the viewpoint of good balance between the hydrophobic and hydrophilic surfaces. Note that a lamellar structure is formed when the copolymerization ratio (Ia) / (Ib) is close to 1/1.

  The block copolymerization of the copolymers (Ia) and (Ib) can be performed by a known polymerization method such as an anion living polymerization method. The weight average molecular weight of the obtained block copolymer is preferably 1,500 or more, more preferably 3,000 or more, particularly preferably 15,000 or more from the viewpoint of providing necessary coating strength, and 1,500,000 or less. Is preferably 150,000 or less, particularly preferably 75,000 or less, from the viewpoint of ensuring appropriate processability (formability and coatability).

  The obtained block copolymer is prepared in the form of a paint or a molding material in the same manner as in forming method 1, and is coated or molded.

(Formation method 3)
(I) a block copolymer or graft copolymer including a primary surface unit A forming segment and a secondary surface unit α forming segment; and (II) a primary surface unit B forming segment and a secondary surface unit β forming segment. A method of forming a multi-surface structure in which a block copolymer or a graft copolymer containing is mixed and a composition obtained by adding a compatibilizing agent thereto is applied or molded.

  This forming method achieves a uniform blend by blending a block copolymer (Ia) and a copolymer (Ib) used as raw materials for the block copolymer in the forming method 2 with a compatibilizing agent, Figure 2 is a method for providing a multi-surface structure of the present invention.

  Therefore, the formation method 2 is the same for the explanation and blending ratio of the block copolymer (Ia) and the copolymer (Ib). Further, the mixing method and the coating or molding method are the same as the forming method 1.

  The compatibilizing agent used in the formation method 3 functions to compatibilize mutually incompatible copolymers, and the block copolymer (Ia) and the copolymer (Ib) are incompatible with each other. Especially effective in cases. By blending the compatibilizing agent, when it is prepared in a paint form, the storage stability is improved, the uniform distribution between the copolymers is improved, and a more advanced and precise multi-surface structure can be formed.

  Examples of the compatibilizing agent include compounds having both a hydrophobic portion and a hydrophilic portion. Specific examples thereof include a block copolymer comprising a segment for forming a primary surface unit A and a segment for forming a primary surface unit B. Specific examples thereof include polypropylene-maleic anhydride block copolymers and ethylene-maleic anhydride block copolymers.

  The blending amount of the compatibilizing agent may be selected depending on the type of the compatibilizing agent and the type of the copolymer, but with respect to 100 parts by weight of the total amount of the block copolymer (Ia) and the copolymer (Ib). 0.01 parts by weight or more, further 0.1 parts by weight or more, particularly 0.5 parts by weight or more, 90 parts by weight or less, more preferably 50 parts by weight or less, and particularly preferably 5 parts by weight or less.

(Formation method 4)
For formation of heterogeneous structured particles and / or secondary surface unit β including a material for forming primary surface unit A and / or primary surface unit B, a portion for forming secondary surface unit α and a portion having affinity for primary surface unit A A method for forming a multi-surface structure in which a composition obtained by mixing particles having different phase structure particles including a portion having an affinity for the primary surface unit B is applied or molded.

  This formation method 4 is a method in which secondary surface units are formed of heterophasic structure particles to form a multi-surface structure of sea-island structure. As a basic method, the surface is formed so that at least one of the primary surface units becomes a sea (matrix) and the heterophasic structure particles including the secondary surface units become islands.

  As the material forming the sea, either one of the primary surfaces A and B (hydrophobic material or hydrophilic material) may be used, or a mixture thereof, or a block including both used in forming methods 1 to 3 A copolymer may be used.

  The heterophasic particles that form the islands include heterophasic particles and / or secondary surface unit β forming portions and primary surface units B that include a portion having an affinity for the secondary surface unit α and the primary surface unit A. It is a heterophasic structure particle including a portion having affinity.

  That is, when a part of the particles have affinity or compatibility with the primary surface unit, the heterophasic structure particles are compatible with and fixed to the primary surface unit with affinity, and are formed in other parts of the particle. The secondary surface units are scattered in the primary surface units to construct the multi-surface structure of the present invention.

  The matrix material may be an organic material or an inorganic material. The heterophasic structure particles may be organic particles or inorganic particles.

  Forming method 4 includes a combination of an organic matrix material and organic heterophasic structure particles and / or inorganic heterophasic structure particles, and a combination of an inorganic matrix material and organic heterophasic structure particles and / or inorganic heterophasic structure particles. Each method will be described below.

(Formation method 4-1)
In the formation method 4, the primary surface unit A and / or the material for forming the primary surface unit B is an organic material.

  As the organic material forming the matrix (sea), a known hydrophilic organic material and hydrophobic organic material can be used in addition to the block copolymer.

  As the hydrophilic organic material, a material having a water contact angle of 40 degrees or less can be suitably employed. Specific examples include hydroxyl group-containing ethylenically unsaturated monomers such as 2-hydroxyethyl (meth) acrylate; vinyl alcohol; carboxyl group-containing ethylenically unsaturated monomers such as acrylic acid and methacrylic acid; and unsaturated groups such as maleic anhydride. Group-containing acid anhydrides; nitrogen-containing ethylenically unsaturated monomers such as N, N-dimethylaminoethyl (meth) acrylate and vinylpyrrolidone; ether group-containing ethylenically unsaturated monomers such as vinyl methyl ether and polyethylene glycol mono (meth) acrylate Homopolymer obtained by radical polymerization of a hydrophilic monomer such as a monomer alone, or other ethylenically unsaturated monomer copolymerizable with the hydrophilic monomer (for example, alkyl ester of (meth) acrylic acid, aromatic vinyl monomer) , Fluorine-containing Nirumonoma, copolymers obtained by radical polymerization of a vinyl silane monomer) and, more for example, polyalkylene glycols such as polyethylene glycol can be exemplified.

  As the hydrophobic organic material for the matrix, those having a contact angle with water of 60 ° or more can be suitably employed. Specific examples include (meth) methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, and the like. Esters of acrylic acid; aromatic vinyl monomers such as styrene and vinyltoluene; olefins such as ethylene, propylene and butylene; tetrafluoroethylene, trifluoroethylene, vinylidene fluoride, trichlorotrifluoroethylene, perfluorooctylethyl (meth) acrylate Fluorine-containing monomers such as: vinyl silane monomers; butadiene: homopolymers obtained by radical polymerization reaction of hydrophobic monomers such as vinyl chloride alone, and other copolymerizable with the hydrophobic monomers In addition to copolymers of ethylenic unsaturated monomers, paraffin, micro static phosphorus waxes, waxes such as petrolatum mentioned as preferable.

  In addition, what can take the form of a polymer among these can be employ | adopted also as a hydrophilic segment and a hydrophobic segment of the block copolymer used by this invention, or a graft copolymer.

  Particularly suitable hydrophobic organic materials include fluorine resin, silicone resin, urethane resin and the like.

  The fluororesin can be selected from conventionally known fluororesins, but is advantageous for weather resistance, coating, solvent solubility, etc., so tetrafluoroethylene (TFE), chlorotrifluoroethylene (CTFE), hexafluoro A copolymer mainly composed of propylene (HFP) is preferable. The following are preferable as these fluororesins (they may overlap).

(1) A copolymer comprising fluoroolefin, cyclohexyl vinyl ether, alkyl vinyl ether and hydroxyalkyl vinyl ether as essential constituents, and a unit based on fluoroolefin, cyclohexyl vinyl ether, alkyl vinyl ether, hydroxyalkyl vinyl ether and other comonomers Of 40 to 60 mol%, 5 to 45 mol%, 5 to 45 mol%, 3 to 15 mol% and 0 to 30 mol%, respectively, measured in an uncured state at 30 ° C in tetrahydrofuran A room temperature-curable fluorine-containing copolymer having an intrinsic viscosity of 0.1 to 2.0 dl / g (described in JP-A-57-34107).

  Specific examples include chlorotrifluoroethylene (CTFE) / cyclohexyl vinyl ether (c-HVE) / ethyl vinyl ether (EVE) / hydroxybutyl vinyl ether (HBVE) copolymer, tetrafluoroethylene (TFE) / c-HVE / EVE / HBVE copolymer, CTFE / c-HVE / isobutyl vinyl ether (i-BVE) / HBVE copolymer, and the like.

(2) Obtained by copolymerizing fluoroolefin, carboxylic acid vinyl ester, alkyl vinyl ether and hydroxyalkyl vinyl ether as essential monomers and, as an optional component, other vinyl monomers copolymerizable with these monomers. Vinyl copolymer (described in JP-A-62-2767).

  Specific examples include hexafluoropropylene (HFP) / EVE / HBVE / Beova 9 (trade name: carboxylic acid vinyl ester manufactured by Shell Chemical Co.) copolymer, HFP / EVE / HBVE / vinyl benzoate (VBz) copolymer weight. Copolymer, CTFE / EVE / HBVE / Beova copolymer, TFE / EVE / HBVE / VBz copolymer, HFP / IBVE / HBVE / vinyl pivalate (PIV) copolymer, HFP / EVE / hydroxyhexyl vinyl ether (HHVE) / P-t butyl vinyl benzoate (VPTBz) copolymer, CTFE / EVE / HBVE / vinyl cyclohexylcarboxylate (VCHC) copolymer, CTFE / EVE / HBVE / PIV copolymer and the like.

(3) Formula:
-CClF-CF ₂ -
35 to 65 mol% of structural units represented by the formula:

(Wherein R ¹ , R ² and R ³ are the same or different and have 1 to 10 carbon atoms) and 5 to 50 mol% of the structural unit represented by the formula:

(Wherein R ⁴ is an alkylene group having 2 to 5 carbon atoms) a fluorine-containing copolymer composed of 1 to 30 mol% of structural units (described in JP-A No. 62-174213).

Specific examples include CTFE / Veoba 10 (trade name: carboxylic acid vinyl ester manufactured by Shell Chemical Co., Ltd.) / HBVE copolymer, CTFE / Veoba 10 / CH ₂ ═CHOCH ₂ (CF ₂ ) ₂ H copolymer, CTFE. / Veova 10 / HBVE copolymer.

(4) Fluoroolefin and alkene and formula:
_{CH 2 = CH-CH 2 -O} -R
(Wherein R is — (CH ₂ CXHO) _n —H, n is an integer of 0 to 6, X is H or CH ₃ ), and includes a hydroxy group-containing allyl ether, fluoroolefin, alkene, and hydroxyl group-containing allyl. A fluorine-containing resin in which the content of units based on ether is 25 to 75 mol%, 10 to 70 mol% and 3 to 40 mol%, respectively (described in JP-A-2-265579).

  Specific examples include CTFE / propylene / ethylene glycol monoallyl ether (EGMAE) / vinyl acetic acid (VAA) copolymer, CTFE / ethylene / EGMAE / VAA copolymer, CTFE / isobutylene / EGMAE / VAA copolymer, CTFE. / Propylene / EGMAE copolymer, CTFE / propylene / allyl alcohol / VAA copolymer, TFE / ethylene / EGMAE / VAA copolymer and the like.

(5) A copolymer comprising 25 to 75 mol% of a fluoroolefin, 10 to 70 mol% of a fatty acid vinyl ester, 3 to 40 mol% of an alkylene glycol monoallyl ether, and 0 to 20 mol% of a carboxyl group-containing vinyl monomer. And a copolymer having a hydroxyl value in the range of 60 to 200 mgKOH / g (described in JP-A-2-298645).

  Specific examples include CTFE / vinyl acetate (VAc) / EGMAE / VAA copolymer, CTFE / VAc / diethylene glycol monoallyl ether / VAA copolymer, CTFE / VAc / EGMAE copolymer, and the like.

(6) (1) Formula (I):
-CF ₂ -CFX- (I)
(Wherein X represents a fluorine atom, a chlorine atom, a hydrogen atom or a trifluoromethyl group), a fluoroolefin structural unit (1),
(2) Formula (II):
—CH ₂ —CR (CH ₃ ) — (II)
Β-methyl-substituted α-olefin structural unit (2) represented by the formula (wherein R is an alkyl group having 1 to 8 carbon atoms):
(3) a structural unit (3) based on a monomer having a chemically curable reactive group,
(4) Structural unit based on monomer having ester group in side chain (4), and (5) Structural unit based on other copolymerizable monomer (5)
The structural unit (1) is 20 to 60 mol%, the structural unit (2) is 5 to 25 mol%, the structural unit (3) is 1 to 45 mol%, and the structural unit (4) is 1 to 45 mol%. And a fluorine-containing copolymer having a number average molecular weight of 1,000 to 500,000 comprising 0 to 45 mol% of the structural unit (5) (however, the total of the structural units (1) + (2) is 40 to 90 mol%) Combined (described in JP-A-4-279612).

Specific examples include CTFE / isobutylene (IB) / HBVE / vinyl propionate (VPi) copolymer, CTFE / IB / hydroxyethyl allyl ether (HEAE) / VAc copolymer, and TFE / IB / HBVE / VPi copolymer. Polymer, CTFE / IB / HBVE / Veoba 9 copolymer, TFE / IB / HBVE / VBz copolymer, CTFE / IB / HBVE / diethyl maleate (DEM) copolymer, TFE / IB / HBVE / Veoba 9 / Dibutyl maleate (DBM) copolymer, CTFE / IB / HBVE / diethyl fumarate (DEF) copolymer, CTFE / IB / HEVE / dibutyl fumarate (DBF) copolymer, HFP / IB / HBVE / VBz Polymer, TFE / 2-methyl-1-pentene (MP) / HBVE / VPi copolymer, T E / IB / HBVE / VPi / CH 2 = CH (CF 2) p CF 3 (p = 1~5) copolymers, TFE / IB / HBVE / VPi / VBz copolymer, CTFE / IB / HBVE / VAc Copolymer, TFE / IB / HBVE / t-butyl vinyl benzoate (VtBz) copolymer, TFE / IB / HBVE / VPi / DEM copolymer, CTFE / IB / HBVE / VBz / DEF copolymer, CTFE / IB / HBVE / VPi / CH 2 = CH (CF 2) p CF 3 (p = 1~5) copolymers, CTFE / MP / HEVE / VPi copolymer, TFE / IB / HBVE / VPi / vinyl acetate (VAA) copolymer, TFE / IB / HEVE / VAc / VAA copolymer, TFE / IB / HBVE / VPi / VBz / crotonic acid (CA) copolymer, TFE / IB / H VE / Beova 9 / CA copolymer, TFE / IB / HBVE / Beova 9 / VBz / CA copolymer, TFE / IB / HBVE / Beova 10 / VtBz / CA copolymer, TFE / IB / HBVE / VtBz / Examples include CA copolymers, TFE / IB / HBVE / DEMTFE / IB / HBVE / DFM / CA copolymers, / CA copolymers, TFE / MP / HBVE / VPi / VAA copolymers, and the like.

  Commercially available products containing fluororesins (1) to (6) include, for example, Zeffle (manufactured by Daikin Industries, Ltd.), Lumiflon (manufactured by Asahi Glass Co., Ltd.), Fluonate (manufactured by Dainippon Ink Co., Ltd.), Cephalal Coat (Manufactured by Central Glass Co., Ltd.).

  Of these fluororesins (1) to (6), the fluorine-containing copolymer (6) is preferred from the viewpoint of weather resistance.

  As organic heterophasic structure particles, hydrophilic (or hydrophobic) monomers are bonded to the surface of hydrophobic (or hydrophilic) polymer particles by a method such as seed polymerization or graft polymerization, and partially hydrophilic (or Examples thereof include particles formed with a portion having affinity for the primary surface unit of (hydrophobic).

  As the heterophasic particles having a portion having an affinity for the hydrophobic primary surface unit A and a portion capable of forming the secondary surface unit α among the inorganic heterophasic particles, the surface of particles such as hydrophilic metal particles or silica is used. By partially coating with a coupling agent or the like, particles that are partially hydrophobized can be exemplified. Moreover, what filled the hydrophobic material into the pore of inorganic porous particles, such as a zeolite, can also be utilized.

  Among the inorganic heterophasic particles, the heterophasic particles having a portion having an affinity for the hydrophilic primary surface unit B and a portion capable of forming the secondary surface unit β include one of the surfaces of particles such as hydrophobic carbon black. By partially coating the part with a coupling agent or the like, particles that are partially hydrophilized can be exemplified. Moreover, what made the hydrophilic material adsorb | suck to the pore of the porous carbon particle etc. can be utilized.

  The particle diameter of the heterophasic structure particles is not particularly limited, but the number average particle diameter of 10 nm or more, more preferably 50 nm or more, is relatively easy to form the heterophasic structure particles and suppresses the aggregation of the particles and uniformly disperses them. In addition, those having a thickness of 100 μm or less, more preferably 30 μm or less, and particularly preferably 10 μm or less are preferable from the viewpoint of easily forming a target multiphase separation structure.

  In the present invention, the number average particle diameter is measured by an electron microscope.

  The mixing ratio of the organic material as the matrix and the heterophasic particles is preferably 0.1 parts by weight or more, more preferably 1 part by weight or more, and particularly preferably 5 parts by weight or more with respect to 100 parts by weight of the organic material. From the point of improving the balance between the hydrophilicity and the hydrophilicity, and it is preferably 100 parts by weight or less, more preferably 50 parts by weight or less, especially 25 parts by weight or less, and especially 15 parts by weight or less from the point that the dispersion can be made uniform. preferable.

  The mixing method of the organic material for matrix formation and the heterophasic structure particles differs depending on whether it is in the form of paint or in the form of molding material.

  In the case of a paint form, for example, a solvent-type paint, a powder paint, or a water-dispersion-type paint may be used, and a conventionally known paint preparation method may be adopted considering the heterophasic structure particles as a filler. . As the coating method and the post-treatment step, those described in the formation method 1 can be adopted.

  Also in the case of using a molding material, a conventionally known molding method may be employed considering the heterophasic structure particles as a filler. As the forming method, the method described in the forming method 1 can be employed.

(Formation method 4-2)
The method for forming a multi-surface structure according to claim 10, wherein the material for forming the primary surface unit A and / or the primary surface unit B is an inorganic material.

  Examples of the inorganic material for forming the matrix include metal oxide sols such as water glass.

  The blending ratio of the inorganic material and the heterophasic particles is such that the heterophasic particles are 0.1 parts by weight or more, more preferably 1 part by weight or more, particularly 5 parts by weight or more based on 100 parts by weight of the inorganic material. It is preferable from the viewpoint of improving the balance of hydrophilicity, and is preferably 100 parts by weight or less, more preferably 50 parts by weight or less, particularly preferably 25 parts by weight or less, and particularly preferably 15 parts by weight or less from the viewpoint of uniform dispersion.

  The mixing method of the inorganic material for matrix formation and the heterophasic structure particles is different depending on whether it is a paint form or a molding material form.

  In the case of a paint form, for example, a solvent-type paint is preferable, and a conventionally known paint preparation method may be adopted considering the heterophasic structure particles as a filler. As the coating method and the post-treatment step, those described in the formation method 1 can be adopted.

  Also in the case of using a molding material, a conventionally known molding method may be employed considering the heterophasic structure particles as a filler. As the forming method, the method described in the forming method 1 can be employed.

  When an inorganic material is used as a matrix (sea), it is particularly advantageous in that a strong and durable film can be formed.

  When used as a paint form, the substrate may be an organic substrate or an inorganic substrate.

  Although the multiple surface structure of the present invention has been described in detail and specifically, various functions and properties may be further imparted to the multiple surface structure of the present invention.

(Antistatic function)
By blending conductive materials such as conductive polymers, metal fillers, carbon nanotubes, etc. and dispersing them on the surface, the antistatic effect of the multi-surface structure can be improved and the adhesion of electrostatic adhesive substances can be further prevented. .

  Further, when a multi-surface structure is formed in which the hydrophilic surface unit is a relatively wide sea, a continuous water film is formed on the hydrophilic surface by surrounding water, and the antistatic effect is improved.

In order to obtain such an excellent antistatic effect, the surface resistance value is desirably 10 ¹² Ω or less.

(Antibacterial and antifungal function)
By adding a metal having an antibacterial and antifungal action such as Ag, Zn and Cu, an antibacterial and antifungal function can be imparted to the multiple surface structure in addition to preventing adhesion.

(Impact resistance)
By blending the rubber component or designing part or all of the organic material or block copolymer to be elastomeric, it is possible to impart elastomericity to the multi-surface structure and improve impact resistance.

  The present invention further relates to an article having a multi-surface structure of the present invention and an article having a multi-surface structure formed by the above forming method.

  Examples of the article of the present invention are listed below, but are not limited to these. Further, the present invention is not limited to the double surface structure, and can be applied to an m-fold (m is an integer of 2 or more) surface structure. The surface unit) and the n-th order surface unit (the next largest surface unit) will be described.

(1) Articles used in an environment where they come into contact with human bodies and living organisms:
(Average maximum width of n + 1 primary surface units)
2-100 nm, preferably 2-40 nm
(Average maximum width of nth order surface unit)
20 times or less, preferably 2 to 10 times, more preferably 2 to 5 times the average maximum width of n + 1-order surface units

(1-1) Articles used in an environment in contact with the human body:
(Types of adhesive substances)
Various blood components (plasma, red blood cells, platelets, white blood cells, etc.), various body fluids (lymph fluid, saliva, tears, sweat, feces, etc.), fat, skin fragments, etc.

  It is also useful as daily necessities such as antithrombotic materials, antiprotein adhesion materials, fat / lipid adhesion prevention materials, urine stone adhesion prevention materials shown below.

(Specific product examples)
Medical-related items:
Artificial blood vessel, blood pack, artificial organ, artificial heart, artificial lung, lung drainage, artificial skin, transdermal device, urine collection pack, urinary catheter, intraocular lens, contact lens, artificial bone, artificial joint, artificial tooth, dental Caries prevention agent (applied to teeth), toilet (not urinary stone) and its connecting tube.
Daily necessities:
Bedding (futon, bed, sheets), towels, gloves (hard to stick), hairdressing tools (comb, scissors, clippers, shaving, dryer), toiletries (toothbrush, bath tub, bathroom mat, bathroom chair) )Such.

(1-2) Articles used in an environment where organisms are likely to adhere:
(Types of adhesive substances)
Algae, spider, various bacteria, etc.

(Specific product examples)
Ship bottom materials, ship bottom paint, ship dogs, exterior wall materials, materials around water (bathrooms, sinks, bathtubs, etc.), tiles, aquariums, irrigation channels, circulating water use facilities (water pipes in general), underwater buildings (dams, Port, embankment, etc.), canals, heat exchangers, air conditioner drain pans, drain hoses, drain pumps, filters, drains, drainage channels, food factories (dairy production lines, tanks, piping, etc.), food storage ( Freezer, refrigerator), food processing equipment (mixer, juicer, noodle making machine, rice cooker, etc.), tableware container, dishwasher, dish dryer, beverage server (beer and juice server, water cooler), show Cases, kitchen counters, water bottles, water tanks, pools, cups, straws, tableware (no cups, pots or teapots with tea astringency), cooking utensils (chopping boards, cups) Nji, kitchen knife), scales, shoes, socks (athlete's foot prevention), washing machine, dryer, such as a can opener.

(2) Articles used in an environment where crystals tend to grow:
A multi-surface structure in which m is 3 or more is preferred.
(Average maximum width of n + 1 primary surface units)
2-100 nm, preferably 2-40 nm
(Average maximum width of nth order surface unit)
20 times or less, preferably 2 to 10 times, more preferably 2 to 5 times the average maximum width of n + 1-order surface units

(2-1) Articles used in an environment where wax or sludge easily adheres:
A sea-island surface structure in which the hydrophilic surface unit is the sea and the hydrophobic surface unit is the island is preferable.
(Types of adhesive substances)
Sludge in refrigeration oil (degraded products of various oils and mineral oils), wax (for example, n-paraffin etc.) components in various oils, and the like.

(Specific product examples)
Filters, refrigerator decompression parts (capillaries, various decompression valves, etc.)

(2-2) Articles used in an environment where scales are likely to adhere:
A sea-island surface structure in which the hydrophilic surface unit is the sea and the hydrophobic surface unit is the island is preferable.
(Types of adhesive substances)
Deposited (for example, crystallized) inorganic substances in water. Many scales crystallize and precipitate in the form of carbonic acid, phosphoric acid, sulfuric acid, calcium salt of silicate or silicate.

(Specific product examples)
Heat exchanger, boiler, cooling tower etc.

(2-3) Articles used in an environment where icing is likely to occur:
A sea-island surface structure in which the hydrophobic surface unit is the sea and the hydrophilic surface unit is the island is preferable.
(Types of adhesive substances)
Water drops, water, ice, snow, etc.

(Specific product examples)
Heat exchanger fins (defrost countermeasures), roofing materials (coated on tiles, etc.), antennas, power transmission lines (preventing cutting and destruction by snow etc.), ship exterior (preventing icing), ice trays, ice machines, refrigerators, Freezer (rooms, cars), glass (various vehicles, buildings), outdoor telecommunications equipment (various antennas such as parabolic antennas, communication towers, communication cables, electric wires, power transmission towers, etc.), transportation vehicles (ships and Decks such as trains, steps to get on and off various vehicles, pantographs, trolley lines, and other external vehicle projections, aircraft wings, and various vehicle exteriors), buildings (exteriors such as roof tiles and tiles), roads, and sidewalks (It is hard to freeze, snow removal and deicing are easy), shoe soles, tires (hard to freeze), salt damage prevention paint, insulators (flashover prevention), etc.

(3) Articles used in an environment exposed to air:

(3-1) Articles mainly used indoors:
There are many adhesive substances having a size of 0.01 to 5 μm, and most of them are environments characterized by being 0.1 to 0.5 μm.
(Average maximum width of n + 1 primary surface units)
2-1000 nm, preferably 2-200 nm, more preferably 5-50 nm
(Average maximum width of nth order surface unit)
20 times or less, preferably 2 to 10 times, more preferably 2 to 5 times the average maximum width of n + 1-order surface units

(Types of adhesive substances)
Oil smoke, cigarette smoke and spears.

(Specific product examples)
Indoor building materials (ceiling materials, wall materials, wallpaper, etc.), blinds, curtains, flooring materials, carpets, transparent materials (lighting covers, glass, show windows, instrument covers, glasses, goggles, etc.), mirrors (mirrors for vehicles, Household, wash mirrors, etc.), heat exchangers, air conditioners (fans, exteriors, etc.), air conditioner ducts, humidification hoses (prevention of allergens such as soot in the room and bacteria), outlets, exhaust outlets, etc. Surroundings, wigs, artificial hair, kitchens, range hoods, clothes (no odor transfer), cosmetics (no odor transfer), etc.

(3-2) Articles mainly used outdoors:
There are many adhesive substances having a size of 0.01 to 50 μm, and this is an environment characterized by the variety of types and sizes.
(Average maximum width of n + 1 primary surface units)
0.01-5 μm, preferably 10-1000 nm, more preferably 10-50 nm
(Average maximum width of nth order surface unit)
20 times or less, preferably 2 to 10 times, more preferably 2 to 5 times the average maximum width of n + 1-order surface units

(Types of adhesive substances)
Dust (about 0.1-50 μm), salt crystals along the coast (about 0.1-10 μm), droplets (about 10-50 μm), automobile exhaust gas, etc.

(Specific product examples)
Outdoor building materials (outer walls of buildings, exteriors of vehicles, ships, aircraft, etc.), road-related members (guardrails, signs, signals, tunnel walls, lighting equipment, sign covers, soundproof walls, elevated bridges, etc.) transparent members (Outdoor lighting cover, glass, signboard cover, show window, greenhouse, solar battery cover, solar water heater cover, instrument cover, glasses, goggles, etc.), mirror (vehicle mirror, road mirror, etc.), heat exchanger, Air conditioners (fans, exteriors, etc.), air conditioner ducts, humidification hoses (indoors, prevention of allergens such as bacteria), outlets, exhaust outlets, their surroundings, chimney interiors, surrounding parts, wigs, Artificial hair, outing clothes (smell does not move), cosmetics (smell does not move), playground equipment (amusement park or park equipment), etc.

(4) Articles used in environments where electrical insulation is required:
If a conductive substance adheres to an article that requires insulation, the conductivity is lowered, causing ignition or a reduction in efficiency.
(Average maximum width of n + 1 primary surface units)
0.01-5 μm, preferably 10-1000 nm, more preferably 10-50 nm
(Average maximum width of nth order surface unit)
20 times or less, preferably 2 to 10 times, more preferably 2 to 5 times the average maximum width of n + 1-order surface units

(Types of adhesive substances)
Various conductive substances, such as carbon and carbides, etc., and the attached substances are impregnated with moisture to become conductive.

(Average maximum width of n + 1 primary surface units)
0.01-5 μm, preferably 10-1000 nm, more preferably 10-50 nm
(Average maximum width of nth order surface unit)
20 times or less, preferably 2 to 10 times, more preferably 2 to 5 times the average maximum width of n + 1-order surface units

(Specific product examples)
Terminal blocks for various electrical and electronic parts, plugs such as magnet plugs, and discharging parts such as electrostatic precipitators and ion generators.

(5) Articles used in an environment where stickers such as stickers are applied:
Adhesiveness (stickiness) is ensured with hydrophilic surface units, and peelability is ensured with hydrophobic surface units. In the surface structure of the present invention, the hydrophilic surface unit and the hydrophobic surface unit are finely and uniformly distributed, so that it is easy to apply when applying a sticker or an adhesive tape, and easy to remove when removing it, after preventing the adhesion of the surface of dirt. The effect is played.

  As a form of the surface structure, a sea-island surface structure composed of a hydrophobic sea and a hydrophilic island is preferable.

(Specific product examples)
Various indoor and outdoor walls, various playground equipment, tunnels, telephone poles, telephone boxes, etc.

  EXAMPLES Next, the present invention will be specifically described with reference to examples. However, the present invention is not limited only to these examples.

Example 1
The following components were stirred and mixed to prepare a solvent-type coating composition.

(Combination)
Primary surface unit forming material:
Poly 2-hydroxyethyl methacrylate segment (contact angle with water of 40 degrees or less (contact angle with water of single polymer)) Weight average molecular weight: 5,000, primary surface unit B) and poly 2-ethylhexyl methacrylate segment (pair Water contact angle 60 ° or more Weight average molecular weight: 20,000 Primary block unit A) block copolymer (a) 100 parts by weight Hydrophobic secondary surface unit β forming material:
Maleic anhydride segment (with a water contact angle of 40 ° or less, weight average molecular weight: 1,000) and a poly-2-ethylhexyl methacrylate segment (with a water contact angle of 60 ° or more. Weight average molecular weight: 4,000) Secondary surface unit β ) Block copolymer (b1) of 20 parts by weight hydrophilic secondary surface unit α-forming material:
Poly 2-hydroxyethyl methacrylate segment (with respect to water contact angle of 40 degrees or less. Weight average molecular weight: 1,000, secondary surface unit α) and poly 2-ethylhexyl methacrylate segment (with respect to water contact angle of 60 degrees or more. Weight average molecular weight: 400) block copolymer (b2) 10 parts by weight solvent:
250 parts by weight of an equivalent mixture of xylene / n-butanol

  This coating composition was spray-coated on a glass plate (150 mm × 80 mm × 5 mm) so that the thickness after drying was 5 μm, to prepare a sample having a multi-surface structure of the present invention.

  When the surface of this sample was examined by the following method, the hydrophobic primary surface unit A composed of the poly-2-ethylhexyl methacrylate segment of the copolymer (a) formed the sea, and the copolymer (b2) The poly 2-ethylhexyl methacrylate segment is compatible, the poly 2-hydroxyethyl methacrylate segment forms a hydrophilic secondary surface unit α as an island, and from the poly 2-hydroxyethyl methacrylate segment of the copolymer (a) The hydrophilic primary surface unit B becomes a sea, the maleic anhydride segment of the copolymer (b1) is compatible with this, and the poly 2-ethylhexyl methacrylate segment forms a hydrophobic secondary surface unit β as an island. It was confirmed that it has a multiple surface structure of sea-island structure.

  This multi-surface structure had the following dimensions and distribution.

(Average maximum width)
Hydrophobic primary surface unit A: about 400 nm
Hydrophilic primary surface unit B: about 150 nm
Hydrophilic secondary surface unit α: about 20 nm
Hydrophobic secondary surface unit β: about 50 nm

(Percentage of the maximum width within the range of 1/3 to 3 times the average maximum width)
Hydrophobic primary surface unit A: 75%
Hydrophilic primary surface unit B: 80%
Hydrophilic secondary surface unit α: 90%
Hydrophobic secondary surface unit β: 85%

Comparative Example 1
The following components were stirred and mixed to prepare a solvent-type coating composition.

(Combination)
Primary surface unit forming material:
Poly 2-hydroxyethyl methacrylate segment (with a water contact angle of 40 degrees or less. Weight average molecular weight: 5,000, primary surface unit B) and poly 2-ethylhexyl methacrylate segment (with a water contact angle of 60 degrees or more. Weight average molecular weight: 20 100 parts by weight of block copolymer (a) of primary surface unit A):
250 parts by weight of an equal amount mixture of xylene / n-butanol This coating composition was spray-coated on a glass plate (150 mm × 80 mm × 5 mm) so that the thickness after drying was 5 μm, and the surface for comparison A sample having a structure was prepared.

  The surface of this sample was examined in the same manner as in Example 1. As a result, the hydrophobic primary surface unit A comprising the poly-2-ethylhexyl methacrylate segment of the copolymer (a) and the hydrophilic primary comprising the poly 2-hydroxyethyl methacrylate segment. It was confirmed that the surface unit B was formed.

  This surface structure had the following dimensions and distribution:

(Average maximum width)
Hydrophobic primary surface unit A: about 380 nm
Hydrophilic primary surface unit B: about 140 nm

(Percentage of the maximum width within the range of 1/3 to 3 times the average maximum width)
Hydrophobic primary surface unit A: 80%
Hydrophilic primary surface unit B: 80%

Example 2
The following components were stirred and mixed to prepare a solvent-type coating composition.

(Combination)
Primary surface unit forming material:
Maleic anhydride segment (with respect to water contact angle of 40 ° or less, weight average molecular weight: 5,000, primary surface unit B) and polystyrene segment (with respect to water contact angle of 60 ° or more, weight average molecular weight: 25,000, primary surface unit A) ) Block copolymer (a) 100 parts by weight hydrophobic secondary surface unit β-forming material:
Blocks of maleic anhydride segment (with respect to water contact angle of 40 degrees or less, weight average molecular weight: 1,000) and polyethylene segment (with respect to water contact angle of 60 degrees or more, weight average molecular weight: 4,000, secondary surface unit β) 20 parts by weight of polymer (b1) hydrophilic secondary surface unit α-forming material:
Block weight of polyacrylonitrile segment (contact angle with water of 40 degrees or less, weight average molecular weight: 2,000, secondary surface unit α) and polystyrene segment (contact angle with water of 60 degrees or more, weight average molecular weight: 1,000) 5 parts by weight of solvent (b2):
250 parts by weight of an equivalent mixture of xylene / n-butanol

  This coating composition was spray-coated on a glass plate (150 mm × 80 mm × 5 mm) so that the thickness after drying was 5 μm, to prepare a sample having a multi-surface structure of the present invention.

  When the surface of this sample was examined by the following method, the hydrophobic primary surface unit A composed of the polystyrene segment of the copolymer (a) formed the sea, and the polystyrene segment of the copolymer (b2) was the phase. And the polyacrylonitrile segment forms a hydrophilic secondary surface unit α as an island, and the hydrophilic primary surface unit B composed of the maleic anhydride segment of the copolymer (a) forms a sea. It was confirmed that the maleic anhydride segment of the copolymer (b1) was compatible, and the polyethylene segment had a multi-surface structure of sea-island structure in which the hydrophobic secondary surface unit β was formed as an island.

  This multi-surface structure had the following dimensions and distribution.

(Average maximum width)
Hydrophobic primary surface unit A: about 450 nm
Hydrophilic primary surface unit B: about 150 nm
Hydrophilic secondary surface unit α: about 20 nm
Hydrophobic secondary surface unit β: about 20 nm

(Percentage of the maximum width within the range of 1/3 to 3 times the average maximum width)
Hydrophobic primary surface unit A: 75%
Hydrophilic primary surface unit B: 80%
Hydrophilic secondary surface unit α: 90%
Hydrophobic secondary surface unit β: 85%

Comparative Example 2
The following components were stirred and mixed to prepare a solvent-type coating composition.

(Combination)
Primary surface unit forming material:
Maleic anhydride segment (with respect to water contact angle of 40 ° or less, weight average molecular weight: 5,000, primary surface unit B) and polystyrene segment (with respect to water contact angle of 60 ° or more, weight average molecular weight: 25,000, primary surface unit A) ) Block copolymer (a) 100 parts by weight solvent:
250 parts by weight of an equal amount mixture of xylene / n-butanol This coating composition was spray-coated on a glass plate (150 mm × 80 mm × 5 mm) so that the thickness after drying was 5 μm, and the surface for comparison A sample having a structure was prepared.

  The surface of this sample was examined in the same manner as in Example 1. As a result, the hydrophobic primary surface unit A comprising the poly-2-ethylhexyl methacrylate segment of the copolymer (a) and the hydrophilic primary comprising the poly 2-hydroxyethyl methacrylate segment. It was confirmed that the surface unit B was formed.

  This surface structure had the following dimensions and distribution:

(Average maximum width)
Hydrophobic primary surface unit A: about 430 nm
Hydrophilic primary surface unit B: about 130 nm

(Percentage of the maximum width within the range of 1/3 to 3 times the average maximum width)
Hydrophobic primary surface unit A: 80%
Hydrophilic primary surface unit B: 85%

Test Example 1: Contamination test with cigarette smoke The sample prepared in Examples 1-2, the sample prepared in Comparative Examples 1-2, and an untreated glass plate (control) were placed on the wall in the smoking room (about 10 m ² ). Standing for 3 months while applying wind with an electric fan, the color difference (ΔE) before and after the start of the test is measured using a photometer (color meter Z2000 manufactured by Nippon Denshoku Industries Co., Ltd.) according to JIS Z8722. We examine from the reflectance.

  The results are shown in Table 1.

Test Example 2: Underwater organism adhesion test The sample prepared in Examples 1-2, the sample prepared in Comparative Examples 1-2, and an untreated glass plate (control) were placed in Lake Biwa (fresh water) in Otsu Port, Otsu City, Shiga Prefecture. Mount it at a depth of 1m and leave it for 3 months. Visually inspect the surface condition before and after the test.

  The results are shown in Table 1.

It is a schematic cross-sectional schematic diagram for demonstrating the multiple surface structure of this invention. It is a schematic cross-sectional schematic diagram for demonstrating the surface structure of a single layer.

Explanation of symbols

1 Hydrophobic primary surface unit A
2 Hydrophilic primary surface unit B
3 Hydrophilic secondary surface unit α
4 Hydrophobic secondary surface unit β
5 Large hydrophobic adhesive substance 6 Small hydrophilic adhesive substance 7 Small hydrophobic adhesive substance 10 Surface unit 11 Surface unit 12 Large adhesive substance 13 Small adhesive substance 14 Distortion

Claims (23)

Non-adhesive multi-surface structure having the following multi-surface structure.
(1) including two types of primary surface units A and B having different water contact angles and a difference in water contact angle of 20 degrees or more,
(2) The primary surface unit A has a secondary surface unit α having a water contact angle different from that of the primary surface unit A in its surface structure, and / or the primary surface unit B is different from the primary surface unit B Including a secondary surface unit β having a contact angle with water in its surface structure,
(3) Adjacent primary surface units have different water contact angles. The multi-surface structure according to claim 1, wherein either one of the primary surface units A or B is a crystalline portion and the other is an amorphous portion. The multi-surface structure according to claim 1 or 2, wherein the secondary surface unit is a surface unit present on the surface of the heterophasic structure particle. The multiple surface structure according to any one of claims 1 to 3, wherein an average maximum width of one primary surface unit is 1 or less and 1/10 or more of an average maximum width of the other primary surface unit. The multi-surface structure according to any one of claims 1 to 4, wherein 50% or more of the maximum width of each primary surface unit and secondary surface unit is in a range of 1/3 to 3 times the average maximum width. 6. The multi-surface structure according to claim 1, wherein at least one of the m-th order surface units (m is an integer of 2 or more) further includes m + 1-order surface units having different water contact angles. (I) a high molecular weight block copolymer or graft copolymer comprising a segment for forming primary surface unit A and a segment for forming primary surface unit B; (II) a segment for forming secondary surface unit α and primary surface unit A; Low molecular weight block copolymer or graft copolymer containing a segment having affinity and / or low molecular weight block copolymer containing a segment having an affinity for secondary surface unit β-forming segment and primary surface unit B The method for forming a multiple surface structure according to any one of claims 1 to 6, wherein a composition obtained by mixing a coalescence or a graft copolymer is applied or molded. (I) a block copolymer or graft copolymer including a primary surface unit A forming segment and a secondary surface unit α forming segment; and (II) a primary surface unit B forming segment and a secondary surface unit β forming segment. The method for forming a multi-surface structure according to any one of claims 1 to 6, wherein a composition containing a block copolymer obtained by copolymerizing a block copolymer or a graft copolymer containing is coated or molded. (I) a block copolymer or graft copolymer including a primary surface unit A forming segment and a secondary surface unit α forming segment; and (II) a primary surface unit B forming segment and a secondary surface unit β forming segment. A method for forming a multi-surface structure according to any one of claims 1 to 6, wherein a block copolymer or a graft copolymer containing is mixed, and a composition obtained by adding a compatibilizer thereto is applied or molded. For formation of heterogeneous structured particles and / or secondary surface unit β including a material for forming primary surface unit A and / or primary surface unit B, a portion for forming secondary surface unit α and a portion having affinity for primary surface unit A The method for forming a multi-surface structure according to any one of claims 1 to 6, wherein a composition obtained by mixing particles having different phase structure particles including a portion having an affinity for the primary surface unit B is applied or molded. The method for forming a multi-surface structure according to claim 10, wherein the material for forming the primary surface unit A and / or the primary surface unit B is an organic material. The method for forming a multi-surface structure according to claim 10, wherein the material for forming the primary surface unit A and / or the primary surface unit B is an inorganic material. An article having a multi-surface structure according to any one of claims 1 to 6. An article having a multi-surface structure formed by the forming method according to claim 7. The article according to claim 13 or 14, which is an article used in an environment in contact with a human body. The article according to claim 13 or 14, which is an article used in an environment to which organisms are likely to adhere. The article according to claim 13 or 14, wherein the article is used in an environment where sludge easily adheres. The article according to claim 13 or 14, wherein the article is used in an environment in which a scale easily adheres. The article according to claim 13 or 14, which is an article used in an environment exposed to indoor air. The article according to claim 13 or 14, wherein the article is used in an environment exposed to outdoor air. The article according to claim 13 or 14, which is an article used in an environment to which water droplets, water, ice and / or snow easily adhere. The article according to claim 13 or 14, which is an article used in an environment where electrical insulation is required. The article according to claim 13 or 14, which is an article used in an environment where affixing is performed.

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