JP2019099649A - Composition for forming three-dimensional structure, and three-dimensional structure formation method - Google Patents

Abstract

To propose a novel composition for forming a three-dimensional structure, capable of self forming a three-dimensional structure having uneven structure consisting of irregular shapes on a surface without adding fine particles or the like, and capable of adjusting size of unevenness as appropriate.SOLUTION: There is proposed a composition for forming a three-dimensional structure by dissolving or suspension dispersing components A and B consisting of a polymer or an oligomer in a mixed solvent Z containing a solvent X and a solvent Y satisfying followings. Solvent X: dissolves the component A and the component B. Solvent Y: dissolves the component A but solubility of the component B is low. Boiling point of the solvent Y is higher than that of the solvent X.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a composition for forming a three-dimensional structure capable of forming a three-dimensional structure such as a concavo-convex structure on a surface, and a method for forming a three-dimensional structure using the composition.

  As a method for forming a three-dimensional structure such as a concavo-convex structure on the surface, for example, in Patent Document 1 (Japanese Patent Laid-Open No. 2004-277534), a pressure-sensitive adhesive and a mixed solvent comprising a good solvent and a poor solvent for the pressure-sensitive adhesive A method is disclosed in which a coating solution to be contained is applied onto a sheet substrate, the mixed solvent is evaporated, and the pressure-sensitive adhesive is phase-separated to form dots.

  Patent Document 2 (WO2015 / 152352) is a pressure-sensitive adhesive film in which a resin layer having adhesiveness is provided on a base material, and an irregular-shaped concave portion is self-formed by containing fine particles in the resin layer. Is disclosed.

  In patent document 3 (Unexamined-Japanese-Patent No. 2016-188344), the curable material which has as a main component alkylated melamine resin (A) which has a C4-C18 alkyl group is apply | coated to a base material, and it hardens | cures. There is disclosed a method of forming irregularities of a random pattern having a high roughening effect on the surface of the cured film.

Unexamined-Japanese-Patent No. 2004-277534 WO 2015/152352 JP, 2016-188344, A

  The present invention is a novel three-dimensional structure that can self-form a three-dimensional structure provided with irregular structures having irregular shapes on the surface without adding fine particles etc., and can appropriately adjust the size of the asperities. The composition for structure formation and three-dimensional structure formation using the same are proposed.

The present invention is a composition for forming a three-dimensional structure, in which mutually incompatible components A and B comprising a polymer or oligomer are dissolved or suspended in a mixed solvent Z containing solvent X and solvent Y satisfying the following: Suggest.
Solvent X: Dissolve component A and component B.
Solvent Y: The component A is dissolved, but the solubility of the component B is low.
The boiling point of the solvent Y is higher than the boiling point of the solvent X.

  The present invention also applies the composition for forming a three-dimensional structure to the surface of a substrate using the composition for forming a three-dimensional structure described above, and heats to volatilize the solvent X prior to the solvent Y, A three-dimensional structure forming method is proposed, characterized in that a component B which hardly dissolves in a solvent Y is precipitated to form a convex portion.

  The composition for forming a three-dimensional structure proposed by the present invention is provided on the surface with a concavo-convex structure having irregular shapes only by applying it to the surface of the substrate and heating to volatilize the solvent X prior to the solvent Y. Three-dimensional structure can be self-formed. That is, it can form by the property which a composition has, without using a cutting apparatus, a type | mold, etc. And the depth of unevenness in the above-mentioned concavo-convex structure can be suitably adjusted by adjusting the selection and the compounding quantity of the material of ingredient A, ingredient B, solvent X and Y.

It is the enlarged image (scale: 703.12 micrometers x 937.42 micrometers) which detected the uneven | corrugated layer surface of the release film (sample) produced in Example 1 by VertScan (trademark). It is the enlarged image (scale: 703.12 micrometers x 937.42 micrometers) which detected the uneven | corrugated layer surface of the release film (sample) produced in Example 2 by VertScan (trademark). It is an enlarged image (scale: 703.12 micrometers x 937.42 micrometers) which detected the uneven layer surface of the release film (sample) produced in Example 3 by VertScan (trademark). It is the enlarged image (scale: 703.12 micrometers x 937.42 micrometers) which detected the uneven | corrugated layer surface of the release film (sample) produced in Example 4 by VertScan (trademark). It is the enlarged image (scale: 703.12 micrometers x 937.42 micrometers) which detected the uneven | corrugated layer surface of the release film (sample) produced in Example 5 by VertScan (trademark). It is the enlarged image (scale: 703.12 micrometers x 937.42 micrometers) which detected the uneven | corrugated layer surface of the release film (sample) produced in Example 6 by VertScan (trademark). It is an enlarged image (scale: 703.12 micrometers x 937.42 micrometers) which detected the uneven layer surface of the release film (sample) produced in Example 7 by VertScan (trademark). It is the enlarged image (scale: 703.12 micrometers x 937.42 micrometers) which detected the uneven | corrugated layer surface of the release film (sample) produced in Example 8 by VertScan (trademark). It is the enlarged image (scale: 703.12 micrometers x 937.42 micrometers) which detected the uneven | corrugated layer surface of the release film (sample) produced in Example 9 by VertScan (trademark). It is a scale figure of the enlarged image in the said FIGS. 1-9, and a white part corresponds to a convex part and a black part corresponds to a concave part in the right vertical band.

  Next, the present invention will be described based on an embodiment. However, the present invention is not limited to the embodiments described below.

<Composition for forming the present three-dimensional structure>
A composition for forming a three-dimensional structure (referred to as a “composition for forming a three-dimensional structure”) according to an embodiment of the present invention is composed of a polymer or an oligomer (these are collectively referred to as “polymer etc.”) The three-dimensional structure-forming composition is obtained by dissolving or suspending the components A and B, which are incompatible with each other, in a mixed solvent Z containing a predetermined solvent X and a predetermined solvent Y.

According to the composition for forming a three-dimensional structure, the composition for forming a three-dimensional structure is applied to the surface of a substrate and heated to volatilize the solvent X prior to the solvent Y, whereby the components A and B are produced. By utilizing the phase separation between the layers, it is possible to self-form a three-dimensional structure provided with an irregular structure having irregular shapes on the surface. Therefore, a three-dimensional structure can be easily formed without using a cutting apparatus, a mold or the like. Here, a three-dimensional structure formed using the present composition for three-dimensional structure formation is referred to as a "present three-dimensional structure".
Moreover, by utilizing the phase separation between the components A and B in this manner, it is possible to form a concavo-convex structure based on a phase separation structure on the order of several μm to several mm.
In addition, when using a method that causes phase separation in the process of distilling off the solvent from the state of being dissolved in the solvent, as described later, it is used by mixing two or more solvents and using the difference in solubility of polymers etc. By forming a concavo-convex structure, the depth of the concavo-convex in the concavo-convex structure can be appropriately adjusted only by selecting a specific polymer or the like and a specific solvent.

  In the present three-dimensional structure formed using the present composition for forming a three-dimensional structure, the component that occupies the most of the components forming the recess is the component A, and the most component of the components forming the protrusion is The component occupied is component B.

(Component A, B)
Component A and component B are preferably incompatible.
From this point of view, it is preferable that the SP value of Component A and the SP value of Component B be lower by 0.01 to 10 than the SP value of Component A. Among them, it is preferable to be low in the range of 0.05 or more or 7 or less, and more preferable to be 0.1 or more or 4 or less.
However, when the concavo-convex structure is formed utilizing phase separation between different polymers etc., the solubility parameter (SP (B)) of component B is 0 more than the solubility parameter (SP (A)) of component A .01-10 may be high.
In addition, if the difference of SP value of the component A and the component B is 0.01, it may become incompatible. For example, when the components A and B are block polymers (graft polymers), they become incompatible with an SP value difference of about 0.01.
The components A and B can be obtained by conventionally known methods.

(Component A)
It is preferable that the component A which will become a main component of a recessed part is a polymer etc. which have predetermined | prescribed SP value and a predetermined | prescribed mass mean molecular weight (Mw).

The component A is incompatible with the component B, and the solubility parameter (SP (A)) is preferably 8 to 21 and is preferably 10 or more, from the viewpoint of mainly forming the concave and convex portions after coating. It is more preferable that it is 20 or less, and more preferably 12 or more or 19 or less.
In addition, from the viewpoint of setting the coating property of the coating solution to be good, the mass average molecular weight (Mw) is preferably 300 to 300,000, and more preferably 2,000 or 200,000 or less. Among these, more preferably 5,000 or more or 100,000 or less.

  Examples of the component A include acrylic polymers such as poly (meth) acrylate, polyesters, polyurethanes, polyolefins, polyethers, polystyrenes, polycarbonates, polyacrylonitriles, polyamides, polyimides and the like. Among them, poly (meth) acrylates are preferable from the viewpoint of easy adjustment of molecular weight and SP value and easy control of the concavo-convex shape. One of these components A may be used alone, or two or more thereof may be used in combination.

  For example, when the component A is an acrylic polymer, in order to increase its SP value, for example, the side chain of the resin of the acrylic polymer may be designed to contain a large number of highly polar functional groups, more specifically For example, homopolymers or copolymers containing structural units such as hydroxy (meth) acrylate having a hydroxyl group, (meth) acrylic acid having a carboxyl group, glycidyl (meth) acrylate having a glycidyl group are mentioned. be able to.

(Component B)
It is preferable that the component B which will become a main component of a convex part is a polymer etc. which have predetermined | prescribed SP value and a predetermined | prescribed mass mean molecular weight (Mw) as mentioned above.
For example, by increasing the blending amount of the component B or increasing the molecular weight of the component B, the area of the projections in the uneven structure can be increased. However, it is not limited to such a method.

The solubility parameter (SP (B)) of the component B is incompatible with the component A, and the solubility parameter (SP (A)) of the component A from the viewpoint of forming mainly the convex portion of the concavo-convex shape after coating. More preferably, it is 0.01 to 10 lower, more preferably 0.05 or more or 7 or less, and particularly preferably 0.1 or more or 4 or less.
From this point of view, the solubility parameter (SP (B)) of the component B is preferably 7 to 20, more preferably 8 or more and 18 or less, and still more preferably 9 or more or 17 or less.

  Further, from the viewpoint of making the coating property of the coating solution good, the mass average molecular weight (Mw) of the component B is 1000 or more larger than the mass average molecular weight (Mw) of the component A, and It is preferably 1300 to 400,000, more preferably 2,000 or more, or 300,000 or less, and more preferably 10,000 or more or 250,000 or less.

  Component B includes, for example, acrylic polymers such as poly (meth) acrylate, polyesters, polyurethanes, polyolefins, polyethers, polystyrenes, polycarbonates, polyacrylonitriles, polyamides, polyimides, etc. Among them, poly (meth) acrylates are preferable from the viewpoint of easy adjustment of molecular weight and SP value and easy control of the concavo-convex shape. One of these components B may be used alone, or two or more thereof may be used in combination.

  For example, when component B is an acrylic polymer, in order to lower its SP value, for example, in the acrylic polymer, the SP value as a monomer and / or oligomer containing one or more (meth) acryloyl groups is You can choose the lower one. Specifically, for example, homopolymers or copolymers containing a structural unit such as alkyl (meth) acrylate having an aliphatic hydrocarbon group and cycloalkyl (meth) acrylate having an alicyclic hydrocarbon group may be mentioned. Can.

  Component B can sufficiently withstand the drying temperature when forming the concavo-convex structure, and from the viewpoint of maintaining the shape, the glass transition temperature of component B is preferably 40 ° C. or higher, and more preferably 50 ° C. or higher. Among them, the temperature is more preferably 60 ° C. or more.

In addition, the said solubility parameter (SP value) is Solubility Parameter, and becomes a scale of solubility. The solubility parameter indicates that the higher the value, the higher the polarity, and the smaller the value, the lower the polarity.
The solubility parameter (SP value) of the component A, the component B and the photocrosslinking initiator C can be measured by a method such as the turbidity method or the Fedors estimation method.

The blending mass ratio of the component A and the component B is preferably 1:99 to 99: 1, and more preferably 5:95 to 95: 5, and more preferably 90:10 to 10:90.
In addition, when two or more types of component A or component B are used, it is set as the mass ratio totaled.

(Crosslinking initiator C)
In the composition for forming a three-dimensional structure of the present invention, a crosslinking initiator C may be dissolved or suspended in the mixed solvent Z in addition to the components A and B.
By blending the crosslinking initiator C to crosslink the three-dimensional structure, the heat resistance of the three-dimensional structure can be enhanced.

  As the crosslinking initiator C, a photocrosslinking initiator, a thermal crosslinking initiator, etc. can be mentioned. Among them, a curing system having fast curing is preferable from the viewpoint of holding the uneven shape formed in the drying step, and a photocrosslinking initiator is preferable from such a viewpoint.

As a photocrosslinking initiator, for example, when applying ultraviolet irradiation as an active energy ray, the photocrosslinking initiator is essential, and the photocrosslinking initiation of benzoin type, acetophenone type, thioxanthone type, phosphine oxide type, peroxide type, etc. is started. Agents can be used.
As a specific example, for example, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-1- [4- (methylthio) phenyl] -2 Morpholinopropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanenone-1 and the like It can be mentioned. These crosslinking initiators may be used alone or in combination of two or more. Among them, UV-curable polyfunctional acrylates are preferred.

  On the other hand, as a thermal crosslinking initiator, an azo initiator and a peroxide initiator can be mentioned, for example.

  The compounding amount of the crosslinking initiator C is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the total amount of the components A and B, and more preferably 0.1 parts by mass or more or 10 parts by mass or less More preferably, it is 1 part by mass or more.

The component A or the component B or both of them may be a resin or resin composition having a crosslinking performance. In that case, crosslinking can be carried out without blending the crosslinking initiator C.
For example, as the photocrosslinkable compound, a compound having a crosslinkable unsaturated bond, specifically, a monomer or an oligomer having an ethylenically unsaturated bond can be mentioned.
Moreover, as a thermosetting resin, a urethane resin, a urea resin, a melamine resin, an acrylic resin, a transparent polyimide precursor varnish etc. can be mentioned, for example.

(Other ingredients)
In the composition for forming a three-dimensional structure of the present invention, other components may be dissolved or suspended in the mixed solvent Z in addition to the component A, the component B and the crosslinking initiator C.
Examples of other components include peeling components, leveling agents, ultraviolet absorbers, organic or inorganic fine particles, and the like.

  Examples of the peeling component, that is, the component having peelability include, in addition to silicone compounds, compounds such as fluorine compounds, olefin compounds and long chain alkyl group-containing compounds. These may be polymers or low molecular weight compounds, and may contain one or more of them.

  The content of the peeling component is preferably 0.5% by mass to 90% by mass, more preferably 1.0% by mass or more or 85% by mass or less, and particularly preferably 2.0% by mass or more or 80% by mass or less Is preferred.

(Solvent X)
The solvent X is preferably a good solvent for the component A, the component B and the crosslinking initiator C. That is, the solvent is preferably capable of dissolving all of the component A, the component B and the crosslinking initiator C.

  The boiling point of the solvent X is preferably 50 ° C to 200 ° C, and more preferably 60 ° C or more or 140 ° C or less, and particularly preferably 70 ° C or more or 120 ° C or less.

  Examples of the solvent X include ketone solvents such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, diisobutyl ketone and cyclohexanone diacetone alcohol; alcohol solvents such as pentanol, hexanol, heptanol and octanol; ethylene glycol monoethyl ether Ether solvents such as ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate; methyl acetate, ethyl acetate, butyl acetate, methoxybutyl acetate, amyl acetate, propyl acetate, ethyl lactate, methyl lactate, lactic acid Ester solvents such as butyl; toluene, xylene, solvent naphtha, hexane, cyclohexane, ethylcyclohexane, methyl Cyclohexane, heptane, octane, organic solvents such as hydrocarbon solvents decane. These organic solvents may be used alone or in combination of two or more.

(Solvent Y)
The other solvent Y is preferably a good solvent for the component A and the crosslinking initiator C and a poor solvent for the component B. That is, Component A and the crosslinking initiator C can be dissolved, but a solvent having low solubility in Component B is preferable.
In addition, the "low solubility" of the component B is a meaning which includes the case where it classify | categorizes into an insolble or swelling (swelling) with respect to the component B.

The boiling point of the solvent Y is preferably 51 ° C. to 201 ° C., and more preferably 61 ° C. or more or 141 ° C. or less, and particularly preferably 71 ° C. or more or 121 ° C. or less.
However, the boiling point of the solvent Y is preferably higher than the boiling point of the solvent X from the viewpoint that the solvent X can be volatilized earlier than the solvent Y, and it is preferably 1 to 80 ° C. in particular, and 2 ° C. among them. As described above, it is more preferable that the temperature be 5 ° C. or higher.
When the solvent Y has a boiling point higher than that of the solvent X, the solvent X is volatilized prior to the solvent Y, and the component B which is difficult to dissolve in the solvent Y precipitates to easily form a convex portion mainly.

In addition, the said solvent X and solvent Y which are used can be selected by the difference in a boiling point. However, it can also be selected by the difference of other characteristics. Specific properties include relative evaporation rates, vapor pressure at a given temperature and pressure, affinity of component A or component B.
For example, from the same viewpoint, that is, from the viewpoint that the solvent X can be volatilized before the solvent Y, the relative evaporation rate of the solvent X is preferably higher than the relative evaporation rate of the solvent Y. Among them, the relative evaporation rate of the solvent X is preferably 1 or more, or preferably not less than the relative evaporation rate of butyl acetate, and the relative evaporation rate of the solvent Y is less than 1 or butyl acetate Preferably it is less than the relative evaporation rate.
In this case, the "relative evaporation rate" is defined as the specific evaporation rate when the evaporation rate of butyl acetate at 25 ° C. under atmospheric pressure is defined as 1. For example, as relative evaporation rates of various solvents, butyl acetate: 1, MEK: 4.52, cyclohexane: 2.9, toluene: 2.66, methoxypropanol: 0.71, n-butanol: 0.39.

  Examples of the solvent Y include alcohol solvents such as methanol, ethanol, butanol, isobutanol and propyl alcohol; ketone solvents such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, diisobutyl ketone and cyclohexanone diacetone alcohol; Ether solvents such as alcohol diethylene glycol monomethyl ether and propylene glycol monomethyl ether; methyl acetate, ethyl acetate, butyl acetate, methoxybutyl acetate, amyl acetate, propyl acetate, ethyl acetate, ethyl lactate, methyl lactate, butyl lactate and other ester solvents; toluene, Carbonized water such as xylene, solvent naphtha, hexane, cyclohexane, ethylcyclohexane, methylcyclohexane, heptane, octane and decane An elemental solvent can be mentioned. These solvents may be used alone or in combination of two or more.

(Solvent Z)
The solvent Z is preferably blended with the solvent X and the solvent Y in a mass ratio of 0.1: 99.9 to 99.9: 0.01, and in particular 1:99 to 99: 1, among which 10:90 to More preferably, it is contained in a mass ratio of 90:10, in particular 15:85 to 85:15, and in particular 80:20 to 20:80.
In addition, when the solvent X or the solvent Y is used 2 or more types, it is set as the mass ratio totaled.

<Method for forming book 3D structure>
As a method of forming a three-dimensional structure using the composition for forming a three-dimensional structure, for example, the composition for forming a three-dimensional structure is applied to the surface of a substrate and heated to be solvent X prior to solvent Y. By volatilizing the component B and depositing the component B that is difficult to dissolve in the solvent Y to form a convex part, thereby forming a three-dimensional structure such as a concavo-convex structure on the surface (referred to as “this three-dimensional structure forming method”) be able to.
According to such a method for forming a three-dimensional structure, it is possible to form a concavo-convex structure provided with irregularly shaped convex portions, and further, component A, component B, crosslinking initiator C, solvents X and Y. The size of the asperities can be controlled by the selection of materials and adjustment of the blending amount.
Thus, using the composition for forming a three-dimensional structure, a cured product of the three-dimensional structure of the composition for forming a three-dimensional structure, a molded article provided with the cured product, or a laminate provided with the cured product Etc can be formed.

  As described above, if a release film provided with a concavo-convex layer having the present three-dimensional structure on the surface is formed on at least one surface side of the substrate, for example, an adhesive film is peelably laminated on the concavo-convex layer By doing this, the uneven structure can be transferred to the adhesive film.

Hereinafter, an example of a more specific embodiment of the three-dimensional structure forming method will be described.
A mixed resin of the component A, the component B and, if necessary, the crosslinking initiator C is a solvent which is a good solvent for a predetermined mixed solvent Z, for example, the component A, the component B and the crosslinking initiator C X and a solvent Y which is a good solvent for the component A and the crosslinking initiator C (that is, a cosolvent for these), a poor solvent for the component B, and having a boiling point higher than the solvent X The mixed solvent Z is added and dissolved to prepare a composition for forming a three-dimensional structure, and the composition for forming a three-dimensional structure is applied to the surface of a substrate. In the process of drying the mixed solvent Z, the solvent X is relatively quickly volatilized, and the proportion occupied by the solvent Y is increased. Therefore, the component B which is difficult to dissolve in the solvent Y is precipitated to form a convex portion. By further drying, a concave part is formed by the component A to form a concavo-convex structure. Alternatively, the concavo-convex structure may be formed by exciting and curing the crosslinking initiator C by light irradiation, for example.

  In the above-mentioned preparation method, as the principle of forming the concavo-convex layer, the environment in the solvent changes as the solvent Z decreases in the process of drying the composition for forming a three-dimensional structure after application. Component A and component B which are incompatible with each other are phase-separated, and the components soluble in both solvents are dissolved in the solvent until drying progresses. It is presumed that the component A which forms a convex portion and is dissolved in both solvents mainly forms a concave portion and a concavo-convex structure is spontaneously formed.

(Base material)
As the substrate, for example, paper, various resin films, a substrate obtained by laminating a paper substrate with a resin, a substrate made of glass, metal foil, a substrate obtained by laminating a metal foil with a resin, etc. can be used. However, it does not limit to these.

  Examples of the paper base include thin paper, medium paper, high quality paper, impregnated paper, coated paper, art paper, sulfuric acid paper, glassine paper and the like.

  Examples of the resin film include polyesters such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate, polyolefins such as polyethylene, polypropylene and polymethylpentene, polycarbonate, polyvinyl acetate, polysulfone, polyetheretherketone, polyethersulfone, polyphenylene The resin film which has various resin, such as a sulfide, a polyether imide, a polyimide, a polyamide, a fluorine resin, a polyvinyl chloride, a polystyrene, a polyurethane, an acrylic resin, as a main component resin can be mentioned. The resin film may be a non-oriented film (sheet) or a stretched film. Among them, a stretched film is preferable, and a biaxial stretched film is more preferable.

As a base material which laminated the above-mentioned paper base material with resin, laminated paper etc. which laminated the above-mentioned paper base material with thermoplastic resins, such as polyethylene, can be mentioned, for example.
Moreover, an aluminum foil etc. can be mentioned as a base material which consists of said metal foil.

Among these, the above-mentioned resin film is preferable because paper powder is not generated at the time of cutting and adhesion of paper powder does not occur also on an adhesive film or the like for transferring the concavo-convex structure, and the easiness of processing, durability, heat resistance It is more preferable that it is a resin film which has polyester as a main component resin, and it is still more preferable that it is a resin film which has a polyethylene terephthalate as a main component resin especially from viewpoints of nature, cost, etc.
Here, the "main component resin" means a resin having the largest content among the resins constituting the base material, specifically, 50% by mass or more, 70% by mass or more, 80% by mass or more among them Among these, the resin which occupies 90 mass% or more (100 mass% is included) is said.

  The substrate may have a single-layer structure, or may have a multilayer structure of two or more layers mainly composed of the same or different resins.

  The thickness of the substrate is preferably selected as appropriate depending on the application. In general, the thickness is preferably 5 μm to 500 μm, more preferably 10 μm or more and 300 μm or less, and still more preferably 15 μm or more and 200 μm or less.

When using a resin film as a base material, it is also possible to contain particles mainly for the purpose of imparting slipperiness.
The type of particles to be contained in the substrate is not particularly limited as long as the particles can be provided with lubricity. For example, inorganic particles such as silica, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, magnesium phosphate, kaolin, aluminum oxide and titanium oxide, as well as acrylic resin, styrene resin, urea resin, phenol resin, epoxy resin, Organic particles such as benzoguanamine resin can be mentioned.

The shape of the particles is also not particularly limited. For example, it may be spherical, massive, rod-like, flat or the like.
Further, there is no particular limitation on the hardness, specific gravity, color and the like of the particles. These series of particles may be used in combination of two or more as needed.

  The average particle diameter of the particles is preferably 5 μm or less, and more preferably 0.1 μm or more or 3 μm or less. When the average particle diameter of the particles is in the above range, the substrate can be provided with an appropriate surface roughness, and good slipperiness and smoothness can be imparted.

  In addition to the above-mentioned particles, the above-mentioned substrate may, if necessary, be a conventionally known antioxidant, heat stabilizer, lubricant, UV absorber, antistatic agent, softener, crystal nucleating agent, dye, pigment and the like. You may contain.

If necessary, a layer having various functions (referred to as a “functional layer”) can be provided on one side or both sides of the substrate. For example, a functional layer can be provided between the base and the uneven layer.
The functional layer may be, for example, an adhesive layer, an antistatic layer, a lubricating layer, a gas barrier layer such as water vapor, a deposition preventing layer of inclusions in a substrate, an ultraviolet absorbing layer, an anti-scratch layer, an antifouling layer, an antibacterial layer, The layer provided with various functions, such as a reflection prevention layer, a gloss layer, a mat | matte layer, an ink receiving layer, a colored layer, a printing layer, can be mentioned.

(Application of composition for three-dimensional structure formation)
As a method for applying the composition for forming a three-dimensional structure to the surface of a substrate, for example, a commonly known method such as a kiss roll coater, a bead coater, a rod coater, a Mayer bar coater, a die coater, or a gravure coater may be employed. it can.

(Dried)
After applying the composition for forming a three-dimensional structure of the present invention, the temperature at the time of drying is 10 ° C. to 150 ° C. from the relationship with the boiling points of the solvents X and Y in order to volatize the solvent X prior to the solvent Y and evaporate. It is preferable to set it, and it is more preferable to set it at 20 ° C. or more or 140 ° C. or less, and more preferable to set it at 40 ° C. or more or 125 ° C. or less. In addition, you may make it dry at normal temperature.
By adjusting the heating temperature, the maximum height difference of the unevenness can be adjusted, and as the heating temperature is lower, the maximum height difference of the unevenness tends to be larger. In general, the solvent has volatility at a temperature lower than the boiling point, and the volatility property changes depending not only on the boiling point but also on the vapor pressure characteristics, the affinity with a polymer, and the like. For this reason, the heating temperature may be set according to the type and blending mass ratio of the polymer and the like used in the concavo-convex layer, the shape of the intended concavo-convex structure, and the like.

(Crosslinking)
After forming the concavo-convex structure by the above heating, if necessary, the crosslinking initiator C may be excited and cured, for example, by light irradiation or the like to form the concavo-convex structure.
For example, if the component A or B has heat crosslinkability, it may be heated to a temperature at which the heat crosslinkability is excited.
In addition, when a photocrosslinking initiator is contained as the crosslinking initiator C, light of a wavelength at which the photocrosslinking initiator is excited may be irradiated.

(This three-dimensional structure)
According to the method for forming a three-dimensional structure of the present invention, a concavo-convex layer having on the surface thereof a concavo-convex structure having a convex part and a portion other than the convex part (referred to as a “concave part”) This three-dimensional structure can be formed.

As this three-dimensional structure, as shown, for example in FIGS. 1-9, when the surface is planarly viewed, it is preferable to form the structure which the said convex part forms an irregular shape. In addition, in FIGS. 1-9, a white part corresponds to a convex part.
Here, "irregular shape" means a shape that does not have a constant rule and period. Specifically, the shape formed only by straight lines, the shape formed by straight lines of the same pattern, the shape combining these, etc. do not correspond to irregular shapes. Further, for example, a shape in which the same shape (pattern) is repeated at regular intervals, such as a shape transferred by an emboss roll, does not correspond to an irregular shape. The irregular shape can typically include a shape due to a sea-island structure that is naturally formed when mixing an incompatible polymer or the like as shown in FIGS. However, it is not limited to such a shape.
By forming the irregular shape as described above, the irregular shape is formed also in the concavo-convex structure transferred to the pressure-sensitive adhesive film as described above, and the concavo-convex structure is difficult to see after adhesion. Can.

Further, as the present three-dimensional structure, when the surface is viewed in plan, the convex portion forms an irregular pattern, for example, a mesh pattern continuously in the peripheral direction, for example, up and down, left and right direction. A configuration may be provided.
When the irregular shape is continuous in the circumferential direction, the size or shape of the irregular shape is not constant, the shape is not repeated, preferably irregular, and the irregular shape is also arranged. Preferably it is irregular.

Further, the convex portions in the three-dimensional structure may be appropriately scattered as a block having an area, may be present intermittently, or may be continuously connected in plan view.
At this time, the largest of the diameters passing through the centers of the X and Y coordinates of the individual convexes is taken as the longest diameter, and the longest diameter of the longest diameter in the measurement region is taken as the largest longest diameter. Do.
The maximum longest diameter of the convex portion makes it possible to make the air escape well when sticking the pressure-sensitive adhesive film to which the concavo-convex shape has been transferred, and from the viewpoint of making the concavo-convex structure inconspicuous after adhesion. The thickness is preferably 1 μm to 1500 μm, more preferably 10 μm or more or 1200 μm or less, particularly 100 μm or more or 1000 μm or less, and still more preferably 300 μm or more or 800 μm.

Moreover, the convex part in this three-dimensional structure may be presenting linear form which continued the length suitably, when it planarly views. From the viewpoint of making air leakage more favorable when sticking the pressure-sensitive adhesive sheet to which the concavo-convex structure has been transferred, it is preferable that the film is continuous up to the film peripheral edge. In the pressure-sensitive adhesive film or the like to which the convex / concave structure has been transferred by the main mold release film, the convex portions in the concave / convex structure form a concave portion. In the adhesive film etc., the escape route of air will also be continuous. However, in this case, there may be a discontinuous portion in a part of the convex portion.
As an example, the case where the irregular shape is continuously forming a mesh pattern by the convex part continuing to the film peripheral edge part can be mentioned as an example.

For example, in the pressure-sensitive adhesive film formed by transferring the concavo-convex structure as described above, the number of the convex portions present in the concavo-convex structure can make the air escape favorably when the pressure-sensitive adhesive film is attached. From the viewpoint of making the uneven structure inconspicuous after adhesion, it is preferably 1 to 1000 per area of 703.12 μm × 937.42 μm, and is preferably 500 or less, more preferably 100 or less. Among them, 10 or less is preferable.
In addition, the said number of convex parts which exist in the said uneven structure can be calculated | required by counting the number of convex parts which appear on the release film surface in unit area, for example using image analysis software.

In the present three-dimensional structure, when the surface is viewed in plan, the lower limit of the area ratio of the convex portion occupied on the surface can be 10% or more, and in particular, 15% or more, 20% or more, particularly 25% or more. Above all, it can be 30% or more. On the other hand, the upper limit of the area ratio of the convex portion can be 90% or less, and can be 85% or less, further 80% or less, particularly 75% or less, and also 70% or less.
The area ratio of the convex portion in the three-dimensional structure can be analyzed by binarizing the surface of the concavo-convex structure into two regions of the concave portion and the convex portion by image analysis.
When the surface of the concavo-convex structure is binarized into two regions of concave and convex portions by image analysis as described above, the entire surface of the concavo-convex structure may be binarized, or the surface of the concavo-convex structure may be binarized. A part may be binarized in multiple places, and the average may be calculated. In that case, it is preferable to find an average of at least three places, at least five places, and at least 10 places.

  In this three-dimensional structure, as a method of increasing the area of the convex portion, for example, adjustment is performed by increasing the compounding amount of the component B which is the main component of the convex portion or increasing the molecular weight of the component B. Can. However, it is not limited to such a method.

Further, the lower limit of the maximum height difference of the unevenness in the three-dimensional structure can be 0.5 μm or more, in particular, 1.0 μm or more, particularly 1.5 μm or more, in particular 2.0 μm or more, particularly 3.0 μm or more Above all, it can be 4.0 μm or more.
On the other hand, the upper limit of the maximum height difference in the present three-dimensional structure is usually 40 μm or less, particularly 35 μm or less, 30 μm or less, 25 μm or less, 20 μm or less, 15 μm or less.
Among them, the maximum height difference of the unevenness of the three-dimensional structure is preferably 0.5 to 15 μm or 15 to 40 μm.

In addition, the maximum height difference of unevenness | corrugation can be adjusted by adjusting the application | coating thickness at the time of forming an uneven | corrugated layer, for example. However, it is not limited to this.
Further, the maximum height difference of the unevenness can be obtained as the maximum value among the difference between the minimum value of the recess and the maximum value around the recess, or the difference between the maximum value of the protrusion and the minimum value around the protrusion.
A specific method for forming the maximum height difference of such unevenness will be described later.

When the composition for forming a three-dimensional structure contains a crosslinking initiator C, in the present three-dimensional structure, component A or component B or both will be crosslinked to contain their cured products.
Whether crosslinked or not is determined by measuring the gel fraction at each site, and the value is preferably more than 0%, particularly 5% or more, and more preferably 10% or more.

<Application of this 3D structure>
As an example of forming the present three-dimensional structure, a release film provided with a concavo-convex layer having the present three-dimensional structure on the surface on at least one surface side of the substrate can be mentioned. However, it is not limited to such a use.

The release film can transfer the uneven structure to the pressure-sensitive adhesive film, for example, by laminating an adhesive film in a peelable manner on the uneven layer having the uneven structure.
Under the present circumstances, when this three-dimensional structure is planarly viewed, the convex part of the said uneven structure is equipped with the structure formed in irregular shape, and the area ratio of the convex part which occupies on the surface of the said uneven structure. Is 10% to 90%, and if the maximum height difference of the concavo-convex structure is 0.5 μm or more, the pressure-sensitive adhesive film has good release of air when it is attached to an adherend. It is possible to make the uneven structure inconspicuous after adhesion.
Therefore, for example, it adheres to a building wall or window, a car decoration or window, an image display unit of a mobile phone or personal computer, etc., for example, a decoration film, an ultraviolet blocking film, a blue light blocking film, a scratch resistant film, a heat resistant film, scattering It can be used as a release film for producing a pressure-sensitive adhesive film having various functions such as a prevention film, a fingerprint and a sebum adhesion prevention film.

<Explanation of the phrase>
In the present specification, when expressing as “X to Y” (X and Y are arbitrary numbers), “preferably greater than X” or “preferably Y” with the meaning of “X or more and Y or less” unless otherwise stated. Also includes the meaning of "smaller".
Also, when expressed as “X or more” (X is an arbitrary number) or “Y or less” (Y is an arbitrary number), “greater than X is preferable” or “preferably less than Y” It also includes the intention.

  In general, “sheet” is thin as defined in JIS, and its thickness is small and flat for length and width, and “film” is generally thicker than its length and width. A thin flat product of extremely small size and optionally limited maximum thickness, usually supplied in roll form (Japanese Industrial Standard JIS K 6900). However, since the boundary between the sheet and the film is not clear and it is not necessary to distinguish between the two in the present invention, in the present invention, even when it is referred to as "film", "sheet" is included and referred to as "sheet". Even in the case of "film" shall be included.

  Hereinafter, the present invention will be described in more detail based on the following examples and comparative examples.

<Mass average molecular weight (Mw)>
The mass average molecular weight (Mw) of each component is a value measured under the following conditions by GPC method.
Equipment: "HLC-8120GPC" manufactured by Tosoh Corporation
Column: "TSKgel Super H3000 + H4000 + H6000" manufactured by Tosoh Corporation
Detector: Differential Refractive Index Detector (RI Detector / Built-in)
Solvent: Tetrahydrofuran Temperature: 40 ° C.
Flow rate: 0.5 ml / min Injection volume: 10 μL
Concentration: 0.2% by mass
Calibration sample: Monodispersed polystyrene Calibration method: polystyrene conversion

<SP value>
The solubility parameter (SP value) of Component A, Component B and photocrosslinking initiator C was estimated by the method proposed by Fedors et al. Specifically, based on "Basic, application and calculation method of SP value" (Hideki Yamamoto, Information Technology Co., Ltd.), each polymer is referred to the estimation method of Fedors among the estimation methods of solubility parameter of the polymer. From the cohesive energy density of each substituent contained in the component: E (J / mol) and the molar molecular volume: V (cm ³ / mol), calculation is made based on the following equation, and the SP value (σ (cal / cm ³ ) I asked for ^1/2 ).
σ ((J / cm ³ ) ^1/2 ) = (ΣEcoh / ΣV) ^1/2
σ (cal / cm ³ ) ^1/2 = σ (J / cm ³ ) ^1/2 /2.0455

<Maximum height difference of asperities, area ratio of projections, number of projections, and maximum longest diameter of asperities>
Using a surface shape measurement system (“VertScan” (registered trademark) R5500 of Hitachi High-Tech Science, Inc.), the uneven surface shape in the 703.12 μm × 937.42 μm area on the surface of the release film (sample) is Interferometric measurements were made, complemented and baseline corrected, and the data read. The magnification of the objective lens at the time of measurement was set to 5 times.

The maximum height difference of the unevenness was obtained as the maximum value among the difference between the minimum value of the recess and the maximum value around the recess, or the difference between the maximum value of the protrusion and the minimum value around the protrusion.
The area ratio of the convex portion was binarized by setting the peak height threshold and the valley height threshold to 0.0 μm using the bearing function, and the area ratio of the convex portion was determined.
The number of convex portions and the maximum longest diameter of the concavo-convex shape were calculated by the particle analysis function under the following measurement conditions. Of the longest diameters detected, the one with the largest value was taken as the maximum longest diameter.

(Particle analysis)
・ Surface correction: Not ・ Analysis: Collision analysis ・ Binarization threshold: 100 nm
・ Particle molding: Not performed ・ Target judgment Height base: Curved surface height: Upper limit 100000 nm, lower limit 0 nm
Maximum diameter: Upper limit 1000 μm, Lower limit 0 μm
Volume: Lower limit 0.0 μm ³
Aspect ratio: Lower limit 0.0

<Convex regularity and convexity continuity>
The surface of the mold release film (sample) is observed by the above-mentioned surface shape measurement system to evaluate whether the shape of the convex portion has a certain regularity or periodicity, and has regularity and periodicity. If not, the convex regularity was evaluated as "irregular".
In addition, the surface of the release film (sample) is observed in the same manner as described above, and the convex portion (white portion) extends from one edge to the opposite edge of the enlarged image (from the upper side to the lower side or from the right side to the left side) ) It was evaluated whether they were connected continuously. The convexity continuity was evaluated as "presence" when the convexity was continuously connected, and "convexity" when the convexity was scattered or intermittently existed.

Example 1
<Material of base material>
Polyester A: chip of polyethylene terephthalate homopolymer (intrinsic viscosity: 0.66 dl / g)
Polyester B: chip of polyethylene terephthalate homopolymer containing 1000 ppm of amorphous silica having an average particle diameter of 2 μm (Intrinsic viscosity: 0.62 dl / g)

Raw materials for coating solution for functional layer
60 parts by mass of a water-dispersed polycarbonate polyurethane resin (Tg: 35 ° C.) having a carboxyl group, 30 parts by mass of a polymer type crosslinking agent in which an oxazoline group is branched to an acrylic resin, silica sol aqueous dispersion (average particle size: 0 6 parts by mass of .07 μm) were mixed to prepare a coating solution for functional layer.

<Raw Material of Composition for Forming Three-Dimensional Structure>
Acrylic polymer A1: Acrylic acid modified product obtained by copolymerizing glycidyl methacrylate, methyl methacrylate and ethyl acrylate at a molar ratio of 98: 1: 1 (mass average molecular weight (Mw): 20,000, SP value: 12.6 , Tg: 32 ° C)
Acrylic polymer B1: copolymer obtained by copolymerizing methyl methacrylate and methyl acrylate at a molar ratio of 99: 1 (mass average molecular weight (Mw): 95,000, SP value: 9.9, Tg: 105 ° C.)
Photopolymerizable compound: dipentaerythritol hexaacrylate (molecular weight: 578, SP value: 10.4)
Photocrosslinking initiator C1: manufactured by IGM Resin, Omnirad 127
Solvent X: methyl ethyl ketone (a solvent capable of dissolving acrylic polymers A1 and B1, having a boiling point of 80 ° C.)
Solvent Y: methoxypropanol (a solvent which dissolves acrylic polymer A1 and B1 does not dissolve, and its boiling point is 120 ° C.)

(Preparation of base material)
The polyester A is used as a raw material for the intermediate layer, the polyester B is used as a raw material for the surface layer, and each raw material is melt-extruded by separate melt extruders to form a two-layer / three-layer amorphous of surface layer / interlayer / surface layer. I got a sheet. Then, the sheet was co-extruded and solidified on a cooled casting drum to obtain a non-oriented sheet.
Then, it was stretched 3.5 times at 90 ° C. in the machine direction (longitudinal direction). Thereafter, the coating solution for a functional layer is coated to a dry thickness of 0.05 μm and then guided to a tenter, and further subjected to a preheating step in a tenter and stretched in a transverse direction at 4.3 ° C. at 120 ° C. Heat treatment was performed at 230 ° C. for 2 seconds to obtain a polyester film as a substrate. The thickness of the obtained polyester film was 50 μm, and the thickness configuration of the surface layer / intermediate layer / surface layer was 5 μm / 40 μm / 5 μm.

(Formation of uneven layer)
As a coating liquid used for formation of a concavo-convex layer, 45 parts by mass of acrylic polymer A1 as component A, 27.5 parts by mass of acrylic polymer B1 as component B, and dipentaerythritol hexamer as a photopolymerizable compound An acrylic polymer mixture containing 27.5 parts by mass of acrylate and 5 parts by mass of a photocrosslinking initiator C1 is mixed at a mass ratio of 72:28 of methyl ethyl ketone as solvent X and methoxypropanol as solvent Y The mixture was dissolved in the mixed solvent Z obtained as described above to prepare a composition for forming a three-dimensional structure having an acrylic polymer mixture concentration of 30% by mass.

  The composition for forming a three-dimensional structure is applied by Meyer bar to the surface of the functional layer of the polyester film as the base material, the solvent X and the solvent Y are volatilized at 70 ° C., and then ultraviolet rays are irradiated with an ultraviolet irradiation device. A film with a concavo-convex layer was produced by forming a concavo-convex layer having a concavo-convex structure on the surface on one surface side of the substrate by photocuring.

(Formation of release layer)
100 parts by mass of a curable silicone resin (manufactured by Shin-Etsu Chemical Co., Ltd., KS-847H) and 1 part by mass of a curing agent (manufactured by Shin-Etsu Chemical Co., Ltd., PL-50T) as a coating solution used for the release layer The ratio was diluted by 1: 1) to prepare a release layer coating solution having a silicone resin concentration of 4% by mass.
The release layer coating solution is applied by Meyer bar to the surface of the uneven layer of the film with the uneven layer, and the release layer is provided by heating to 120 ° C. for drying and curing, and a release film 1 (sample) is obtained. Made.

Example 2
A release film 2 (sample) was produced in the same manner as in Example 1 except that the thickness of the concavo-convex layer was changed by changing the number of Meyer bars and changing the thickness of the concavo-convex layer to 8 μm.

[Example 3]
A release film 3 (the same method as in Example 1), except that 3% by mass of a silicone-modified acrylic polymer (manufactured by Kyoeisha Chemical, GL04R) was further added to the composition for forming a three-dimensional structure instead of providing a release layer. A sample was prepared.

Example 4
When producing a composition for forming a three-dimensional structure, the above acrylic polymer A1, the above acrylic polymer B1 and dipentaerythritol hexaacrylate as a photopolymerizable compound (mass average molecular weight (Mw): 578, SP value: 10.4 The acrylic polymer mixture is prepared by mixing 60: 20: 20 parts by weight of a mixture ratio of (a) with methyl ethyl ketone as solvent X and methoxypropanol as solvent Y at a mass ratio of 63: 37. A release film 4 (sample) was produced in the same manner as in Example 1 except that it was dissolved in the mixed solvent Z.

[Example 5]
A release film 5 (sample) was produced in the same manner as in Example 1 except that a concavo-convex layer was formed using the composition for three-dimensional structure formation prepared as follows.
That is, as a coating liquid used for formation of a concavo-convex layer, graft copolymer B2 (mass average molecular weight (Mw): 16,000, SP as component B which uses polydimethylsiloxane as a branch polymer and an acrylic monomer as a base polymer) Value: 10.9) 65 parts by mass, acrylic polymer B1 as component A (mass average molecular weight (Mw): 95,000, SP value: 9.9) 35 parts by mass, photocrosslinking initiator C (IGM Obtained by mixing an acrylic monomer mixture containing 5 parts by mass of Opinrad 127, manufactured by resin, with methyl isobutyl ketone as solvent X, methyl ethyl ketone and methoxypropanol as solvent Y in a mass ratio of 28:26:46. The resulting mixture was dissolved in the mixed solvent Z to prepare a composition for forming a three-dimensional structure having a concentration of the acrylic polymer mixture of 16% by mass.

The graft copolymer B2 having the above acrylic monomer as a main polymer comprises 10: 10: 20: 60 of methyl methacrylate, stearyl methacrylate, a silicon macromer having a terminal methacryloyl group having a molecular weight of 5,000, and glycidyl methacrylate. It was an acrylic acid modified product copolymerized at a molar ratio.
The methyl isobutyl ketone and methyl ethyl ketone as the solvent X are solvents capable of dissolving the graft copolymer B2 and the acrylic polymer A1, and the boiling points thereof were 116 ° C. for methyl isobutyl ketone and 80 ° C. for methyl ethyl ketone.
On the other hand, methoxypropanol as the solvent Y is a solvent capable of dissolving only the graft copolymer B2 and the acrylic polymer A1 and has a boiling point of 120 ° C.

[Example 6]
A release film 6 (sample) was produced in the same manner as in Example 5 except that the thickness of the uneven layer was changed by adjusting the Meyer bar to make the maximum uneven height difference 1 μm.

[Example 7]
A release film 7 (sample) was produced in the same manner as in Example 2 except that the three-dimensional structure-forming composition prepared as follows was used and heat drying was performed at 40 ° C. to form an uneven layer.
That is, 50 parts by mass of dipentaerythritol hexaacrylate (mass average molecular weight (Mw): 578, SP value: 10.4) as component A as a coating solution used for forming the uneven layer, polypropylene as component B (Idemitsu Kosan Manufactured by “S400”, mass average molecular weight (Mw): 45,000 (catalog value), SP value: 8.2, Tg: 50 ° C. 50 parts by mass and photocrosslinking initiator (2-hydroxy-2-methyl-) A mixed solvent obtained by blending a mixture containing 3 parts by mass of 1-phenyl-propan-1-one) in a mass ratio of 49: 49: 2 with cyclohexane as solvent X, toluene and methoxypropanol as solvent Y It was made to melt | dissolve in (solvent Z), and the said composition density | concentration prepared the composition for three-dimensional structure formation which is 15 mass%.
Cyclohexane and toluene as the solvent X are solvents capable of dissolving the components A and B, and the boiling points thereof were 81 ° C. and 111 ° C., respectively.
On the other hand, methoxypropanol as the solvent Y is a solvent capable of dissolving only the component A among the components A and B, and its boiling point is 118 ° C.

[Example 8]
A release film 8 (sample) was produced in the same manner as in Example 7 except that the three-dimensional structure-forming composition prepared as follows was used and heat drying was performed at 50 ° C. to form an uneven layer.
That is, as a coating liquid used for formation of an uneven | corrugated layer, the urethane acrylate as a component A (The brand name "U-15HA" by Shin-Nakamura Chemical Co., Ltd. make, mass mean molecular weight (Mw): 2205, SP value: 11.2) 50 parts by mass, 50 parts by mass of polypropylene as component B ("S400" manufactured by Idemitsu Kosan Co., Ltd., mass average molecular weight (Mw): 45,000 (catalog value), SP value: 8.2, Tg: 50 ° C) A mixture containing 3 parts by mass of a crosslinking initiator (2-hydroxy-2-methyl-1-phenyl-propan-1-one), cyclohexane as a solvent X, toluene, and methoxypropanol as a solvent Y 49: 49: It was made to melt | dissolve in the mixed solvent (solvent Z) obtained by mix | blending by the mass ratio of 2, and the said composition density | concentration prepared the composition for three-dimensional structure formation which is 15 mass%.

[Example 9]
A release film 9 (sample) was produced in the same manner as in Example 7 except that the three-dimensional structure forming composition prepared as follows was used and heat drying was performed at 50 ° C. to form a concavo-convex layer.
That is, as a coating liquid used to form the uneven layer, 50 parts by mass of an acrylic polymer A1 (mass average molecular weight (Mw): 20,000, SP value: 12.6, Tg: 32 ° C.) as component A, component B Hydrogenated end acrylate polybutadiene (Nippon Soda Co., Ltd. “TEAI-1000”, mass average molecular weight (Mw): 2,000 (catalog value), SP value: 9.9, Tg: −14 ° C. (catalog value)) 25 parts by mass, 25 parts by mass of dipentaerythritol hexaacrylate (mass average molecular weight (Mw): 578, SP value: 10.4), and a photocrosslinking initiator (2-hydroxy-2-methyl-1-phenyl-propane-1) A mixture containing 5 parts by mass of cyclohexane, toluene, methyl ethyl ketone as solvent X, methoxypropanol as solvent Y, n- The ethanol 6: 25: 32: 31: 6 weight ratio were dissolved in a mixed solvent obtained by mixing in the premixing concentration to prepare a three-dimensional structure forming composition is 15% by mass.

Comparative Example 1
A mold release was carried out in the same manner as in Example 1 except that a mold release layer was provided in the same manner as in Example 1 without forming an uneven layer on the surface of the polyester film as the base film used in Example 1. Film 10 (sample) was produced.

Comparative Example 2
Release paper in which polyethylene is laminated, maximum height difference is 8.2 μm, convex part width is 40 μm, pitch is 310 μm period, convex part has a lattice shape, and silicone release layer is provided on the surface Was used.

(Discussion)
From the results of the above Examples and Comparative Examples and the test results that the present inventor has conducted so far, Component A and Component B are mixed with Solvent X, which is a good solvent for Component A and Component B, and Component A To a mixed solvent Z with a solvent Y which is a good solvent (that is, a co-solvent for these), a poor solvent for the component B, and a boiling point higher than that of the solvent X A composition for forming a structure is prepared, and the composition for forming a three-dimensional structure is applied to the surface of a substrate, and heated to volatilize solvent X prior to solvent Y to volatilize component B, which is difficult to dissolve in solvent Y Can be deposited to form a convex portion, a three-dimensional structure having an irregular structure having irregular shapes on the surface can be self-formed, and component A, component B, solvents X and Y By adjusting the selection of materials and the compounding amount, It was found that it is possible to appropriately adjust the depth of the convex.

Claims (10)

A composition for forming a three-dimensional structure, in which mutually incompatible components A and B comprising a polymer or oligomer are dissolved or suspended in a mixed solvent Z containing a solvent X and a solvent Y satisfying the following.
Solvent X: Dissolve component A and component B.
Solvent Y: The component A is dissolved, but the solubility of the component B is low.
The boiling point of the solvent Y is higher than the boiling point of the solvent X.   In addition to the components A and B, a crosslinking initiator C is further dissolved or suspended in the mixed solvent Z, the solvent X dissolves the crosslinking initiator C, and the solvent Y dissolves the crosslinking initiator C The composition for three-dimensional structure formation according to claim 1, characterized in that.   The SP value (A) of the component A is 8 to 21, the SP value (B) of the component B is 7 to 20, and the SP value (A) −the SP value (B) = 0.01 The composition for forming a three-dimensional structure according to claim 1 or 2, characterized in that   The mass average molecular weight (Mw) of the component A is 300 to 300,000, and the mass average molecular weight (Mw) of the component B is 1000 or more larger than the mass average molecular weight (Mw) of the component A, and 1300 to 1000 It is 400,000, The composition for three-dimensional structure formation in any one of the Claims 1-3 characterized by the above-mentioned.   The composition for forming a three-dimensional structure according to any one of claims 1 to 4, wherein the difference between the boiling point of the solvent X and the boiling point of the solvent Y is 1 to 80 ° C.   A cured product of the composition for forming a three-dimensional structure according to any one of claims 1 to 5.   The molded object provided with the hardened | cured material of the composition for three-dimensional structure formation in any one of Claims 1-5.   The laminated body provided with the hardened | cured material of the composition for three-dimensional structure formation in any one of Claims 1-5.   The composition for forming a three-dimensional structure according to any one of claims 1 to 5 is applied to the surface of a substrate, and heated to volatilize the solvent X earlier than the solvent Y, and the component B hardly soluble in the solvent Y A method of forming a three-dimensional structure, comprising depositing to form a convex portion. 10. The three-dimensional structure forming method according to claim 9, wherein the solvent X is volatilized to form a convex portion, and then the crosslinking initiator C is excited to cause a crosslinking reaction to cure the convex portion.