JP7100846B2 - Manufacturing method of molding mold - Google Patents

Description

The present invention relates to a method for producing a molding mold (mold) containing an olefin polymer.

Olefin polymers are industrially produced by various methods due to their high industrial utility value, and are said to have an annual production volume of over 100 million tons. Since the olefin polymer contains carbon and hydrogen as main components, it is also characterized by being a stable and inexpensive material. On the other hand, the structure having no functional group in the olefin polymer has poor affinity with polar materials and also has properties such as colorability and adhesiveness that are difficult to modify. Further, since the olefin polymer is mainly used as a thermoplastic resin, there is a tendency that many articles made of olefin polymers, for example, molding dies, do not have a sufficient heat resistant temperature for use as a molding dies. ..

As a method for modifying an olefin polymer (method for introducing a functional group), a method of grafting maleic anhydride with a radical generator is known, but these methods are accompanied by a decrease in molecular weight or a cross-linking reaction. There is also a limit to the amount of functional groups that can be introduced. As a solution to this, there is an example of a modification method in a solid phase reaction. (For example, Patent Document 1)

On the other hand, 4-methyl-1-pentene polymers and cyclic olefin (open ring) polymers are known as olefin polymers having a melting point and a glass transition temperature of more than 150 ° C. These resins may be used for mandrel applications. Further, it has been reported that among cyclic olefin polymers, a polymer containing fluorine has been developed and used for nanoimprint film applications. (Patent Documents 2 and 3)

International Publication No. 2015/166939 Pamphlet International Publication No. 2010/098102 Pamphlet International Publication No. 2011/024421 Pamphlet

However, it seems that the current situation is that problems such as a decrease in the molecular weight of the olefin polymer cannot be sufficiently solved. A decrease in molecular weight or structural change may lead to various negative factors such as a decrease in strength as a material. For example, in the case of a molding mold made of an olefin polymer, it may lead to a decrease in durability as well as strength. be.

On the other hand, depending on the use of the olefin polymer, for example, only a part of the molded product of the olefin polymer may be modified. For example, in the case of the molding mold, it is natural to consider that it is preferable to have a high degree of mold releasability only on the surface in contact with the resin to be molded. The same applies to mandrel applications.

If only the surface of the molding die or only a specific place can be modified, the present inventors can modify the molding die while suppressing a decrease in the strength of the molding die, particularly when the molding die is a film or a sheet. We thought that it would be possible to enhance the effect.

It is an object of the present invention to provide a method for efficiently producing a molding mold containing an olefin polymer and preferably mainly modified with a specific site.

As a result of the research conducted by the present inventors in order to solve the above-mentioned problems, it has become possible to efficiently, preferably preferably, modify mainly a specific part of the molding die by means as shown below. It has become possible to provide a new molding mold. That is, the present invention is as follows.

[1]
Atoms (α) of elements selected from Group 15 and Group 16 elements and atoms (β) of Group 17 elements in one molecule are atomized in atomic number ratio: atom (α): atom (β) = 1: 1 to 1. The step 1 of irradiating a radical contained in a ratio of 4: 1 with light is included.
A method for producing a molding mold, which comprises modifying a molding base material containing an olefin polymer having a melting point and / or a glass transition temperature of 70 ° C. or higher and 300 ° C. or lower.

[2]
The step 1 is
In an environment where the molding base material and the radical coexist
The method for producing a molding mold according to the above [1], which is a step of irradiating the radical with light to modify the molding mold base material.

[3]
The method for manufacturing a molding mold according to the above [2], wherein the step 1 is a step of irradiating the molding base material and the radical with light.

[4]
The method for producing a molding die according to any one of the above [1] to [3], wherein a part of the molding die is in an unmodified state.

[5]
The method for producing a molding mold according to any one of the above [1] to [4], wherein the olefin polymer is a fluorine-containing olefin polymer.

[6]
The method for producing a molding mold according to any one of the above [1] to [5], wherein the radical is a chlorine dioxide radical.

[7]
The method for producing a molding die according to any one of [1] to [6] above, wherein the molding die is a nanoimprint molding die.

According to the production method of the present invention, it is expected that mainly the surface or a specific site of the molding mold containing the olefin polymer can be efficiently modified. Therefore, it is possible to suppress a decrease in molecular weight when the molding die, especially the molding die is a film or a sheet, and the molding die having excellent modifiableness and designability while making the best use of the original characteristics of the molding die, especially the molding die. It is considered that a film-shaped or sheet-shaped molding mold can be provided.

FIG. 1 is a schematic schematic diagram for explaining the operation of the embodiment.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited by the following description.
In the present invention, the term sheet may include the meaning of film.

The method for manufacturing a molding mold according to the present invention is as follows.
Atoms (α) of elements selected from Group 15 and Group 16 elements and atoms (β) of Group 17 elements in one molecule are atomized in atomic number ratio: atom (α): atom (β) = 1: 1 ~ 1. The step 1 of irradiating a radical contained in a ratio of 4: 1 with light is included.
It is a method for producing a molding mold obtained by modifying a molding base material containing an olefin polymer having a melting point and / or a glass transition temperature of 70 ° C. or higher and 300 ° C. or lower.
In the present invention, for convenience, the molding mold before modification is referred to as "molding mold base material", and the molding mold after modification is referred to as "molding mold".

The step 1 is preferably a step of irradiating the radical with light to modify the molding base material in an environment where the molding base material and the radical coexist.
In step 1, the molding base material and the radicals are preferably irradiated with light.

"The molding base material and the radical are irradiated with light" is not intended to irradiate the molding base material and the radical independently with light, for example, one. It means that the molding base material and the radicals are irradiated with the light from the light source. Further, it is preferable that the molding base material and the radicals are irradiated with light at the same time.

As will be described later, not only the portion of the molding base material irradiated with light is denatured, but the peripheral portion and the deep layer portion thereof may also be denatured.
Another aspect of the production method of the present invention is to irradiate the system containing radicals with light and then bring the system into contact with the molding base material to modify the molding base material.

The radical contains an atom (α) of an element selected from Group 15 and Group 16 elements and an atom (β) of a Group 17 element in a specific composition ratio.
The radical may contain two or more types of group 15 element atoms, may contain two or more group 16 element atoms, and may contain one or more group 15 element and group 16 element atoms, respectively. It may contain two or more kinds of atoms of Group 17 elements. However, in these cases, the atomic number ratio is the ratio of the total number of atoms of Group 15 and Group 16 elements to the total number of atoms of Group 17 elements.

The element selected from the Group 15 element and the Group 16 element preferably includes nitrogen, oxygen and sulfur, and particularly preferably oxygen.
Preferred group 17 elements include chlorine, bromine and iodine, with chlorine and bromine being even more preferred. Radicals containing chlorine are more preferable because they are easily available or generated. When a radical containing chlorine is used, light containing ultraviolet rays is preferable as the light irradiated in step 1, and when a radical containing bromine or iodine is used, it is considered that the reaction can proceed even with light having a wavelength longer than that of ultraviolet rays. .. Therefore, bromine and iodine are preferable depending on the situation, such as the degree of freedom in light selection and the possibility of photodegradation of the olefin polymer constituting the molding base material.

The atomic number ratio (atom (α): atom (β)) of the radical is preferably 1: 1 to 2: 1, more preferably 1: 2. From the above viewpoint, the chlorine dioxide radical is preferable as the radical. It is considered that chlorine radicals (Cl.) And oxygen molecules (O ₂ ) are generated by irradiating the chlorine dioxide radicals (ClO ₂ ) with light.

In the production method of the present invention, as the olefin polymer constituting the molding base material, known ones can be used without limitation as long as the melting point and / or the glass transition temperature is 70 ° C. or higher and 300 ° C. or lower.

A preferable lower limit of the melting point and / or the glass transition temperature is 80 ° C. On the other hand, the preferred upper limit of the melting point and / or the glass transition temperature is 250 ° C., further 200 ° C., particularly 150 ° C.
The melting point and the glass transition temperature are measured by the following method or an equivalent method using a differential scanning calorimetry device (DSC device).

Using a DSC-50 type differential scanning calorimeter manufactured by Shimadzu Corporation, a sample of about 5.0 mg was heated from 30 ° C. to 320 ° C. at a heating rate of 10 ° C./min under a nitrogen atmosphere, and at that temperature for 10 minutes. Hold. (However, in the case of a polymer that decomposes in the temperature range of 250 ° C. or higher and 320 ° C. or lower, the temperature to be held may be appropriately adjusted to a low temperature as in the conventional method.) Further, the temperature lowering rate is 10 ° C./min to 30 ° C. After cooling and holding at that temperature for 5 minutes, the temperature is raised to 320 ° C. at a heating rate of 10 ° C./min. The endothermic peak observed during this second temperature rise is defined as the melting peak, and the temperature at which the melting peak appears is determined as the melting point (Tm). When the melting peak is multimodal, the melting point is the temperature at which the melting peak on the highest temperature side appears.

Further, the glass transition temperature (Tg) is perceived as the DSC curve bends due to the change in the specific heat and the baseline moves in parallel when the temperature is raised for the second time. The temperature at the intersection of the tangent of the baseline, which is lower than this bending, and the tangent of the point where the inclination is maximum at the bending portion is defined as the glass transition temperature (Tg). However, depending on the form and history of the sample to be used, Tm or Tg at the time of the first temperature rise may be adopted.

Other differential scanning calorimeters may be used as long as they are confirmed to give the same results as the above device.
Specific examples of the olefin polymer include an olefin polymer having a branched structure such as poly4-methyl-1-pentene, a copolymer of a cyclic olefin and an α-olefin, and a ring-opened metathesis polymer of a cyclic olefin. (Ring-opened olefin metathesis polymer), a hydrogenated product thereof, and the like can be exemplified.

Among these, the ring-opening olefin metathesis polymer can be mentioned as a preferable example. Furthermore, a structure containing fluorine is preferable from the viewpoint of shape stability and releasability. Examples of commercially available products of the ring-opening olefin metathesis polymer containing fluorine include FROMP (registered trademark) (manufactured by Mitsui Chemicals, Inc.).

The ultimate viscosity [η] of these polymers in decalin at 135 ° C. may be in the range of 0.5 to 20 dl / g, more preferably 0.8 to 18 dl / g, still more preferably 1 to 15 dl / g. preferable.

The range of preferable molecular weights (weight average molecular weights) of these polymers is preferably 5,000 to 1,000,000, and more preferably 10,000 to 300,000. The above molecular weight can be determined by gel permeation chromatography (GPC method). For example, in the case of the above-mentioned fluorine-containing cyclic olefin polymer, the following method is a preferable method for measuring the molecular weight.

A method for measuring the weight average molecular weight (Mw) and the number average molecular weight (Mn) of a polymer dissolved in tetrahydrofuran (THF) or trifluoromethyltoluene (TFT) by calibrating the molecular weight with a polystyrene standard. Specifically, it is as follows.

Detector: RI-2031 and 875-UV manufactured by JASCO Corporation or Model 270 manufactured by Viscotec, series-connected column: Shodex K-806M, 804, 803, 802.5, column temperature: 40 ° C., flow rate: 1.0 ml / min , Sample concentration: 3.0-9.0 mg / ml.

There are many reports on the means for obtaining such olefin polymers, and they can be adopted without limitation. Further, the 4-methyl-1-pentene polymer is disclosed in, for example, Pamphlet No. 2006/054613 of International Patent Publication No. 2006. Fluorine-containing ring-opening olefin metathesis polymers are disclosed in International Patent Publication No. 2010/098102 and International Patent Publication No. 2011/024421.

The molding base material used in the present invention can be produced by a known method. As a manufacturing method, for example, when the molding base material is in the form of a film or a sheet, extrusion molding (T-die molding, etc.), inflation molding, cast molding (including the case where a spin coating method is also used), etc. are performed. It can be mentioned as a typical example. These methods are preferably used when, for example, a mold such as a nanoimprint method is used. A description of the nanoimprint method is disclosed in the above-mentioned Patent Documents 2 and 3. On the other hand, in the case of a mold having a three-dimensional tendency such as a mandrel, injection molding or extrusion molding is often used.

Typical examples of the olefin polymer constituting the molding mold obtained by the production method of the present invention include a hydroxy group, a carboxy group, an aldehyde group, a carbonyl group, an ether bond, an ester bond, —C (= O) OOH, and the like. And at least one functional group selected from the group consisting of —O—O— is introduced.

The light irradiation is performed on the radicals present in the aqueous phase, the organic phase or the gas phase. When emphasizing the points such as reducing the load on the environment and the influence on the human body, it is preferable to perform the radical on the aqueous phase or the gas phase. In one embodiment, step 1 may be in an environment in which two or more layers of an aqueous phase, an organic phase and a gas phase are present. Further, for example, when the radical is present in the liquid phase, the molding base material may also be present in the liquid phase, but may also be present in another phase, for example, the gas phase.

The concentration of radicals containing atoms (α) and atoms (β) in the aqueous phase and / or the organic phase is not particularly limited, but is, for example, 0.0001 mol / L or more, for example, 1 mol / L or less.

When the molded body mold base material is immersed in the aqueous phase or the organic phase, the amount of the molded body mold base material used in the aqueous phase or the organic phase is not particularly limited, but is relative to the aqueous phase or the organic phase. For example, it may be 1 g / L or more, or 10 g / L or less.

The aqueous phase is not particularly limited as long as it contains water.
The organic phase is not particularly limited as long as it contains an organic solvent.
The organic solvent may be used alone or in combination of two or more. Examples of the organic solvent include a hydrocarbon solvent and a halogenated solvent.

The hydrocarbon solvent is not particularly limited, and examples thereof include n-hexane, cyclohexane, benzene, toluene, o-xylene, m-xylene, and p-xylene.

The halogenated solvent is not particularly limited, and examples thereof include methylene chloride, chloroform, carbon tetrachloride, carbon tetrabromide, and a fluorous solvent.
The fluorous solvent refers to a solvent in which all or most of the hydrogen atoms of the hydrocarbon are replaced with fluorine atoms. The fluorus solvent may be, for example, a solvent in which 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more of the hydrogen atom number of the hydrocarbon is substituted with a fluorine atom.

Examples of the fluorous solvent include, for example, CF _3- (CF ₂ ) _n -CF ₃ (n is 4 to 7), N-((CF ₂ ) _n CF ₃ ) ₃ (n is 1 or 4), hexa. Fluorobenzene, 1- (trifluoromethyl) undecafluorocyclohexane, 1- (trifluoromethyl) pentafluorobenzene, octadecafluorodecahydronaphthalene, among which, for example, CF ₃ (CF ₂ ) ₄ CF ₃ Is preferable.

The fluorous solvent has the advantage that, for example, the reactivity of the solvent itself is low, so that side reactions can be suppressed or prevented. Examples of the side reaction include an oxidation reaction of a solvent, a hydrogen extraction reaction and a chlorination reaction of a solvent by a radical, and a reaction of a radical derived from an olefin polymer constituting the molding base material and the solvent. Be done.

Further, the aqueous phase and / or the organic phase may or may not contain components other than the radicals. The other components are not particularly limited, and examples thereof include the source of the radical, Bronsted acid, Lewis acid, and oxygen (O ₂ ).

One of these may be used, or two or more thereof may be used.
The other components may or may not be dissolved in the aqueous phase and / or the organic phase.
In addition, one substance may also serve as Lewis acid and Bronsted acid. "Lewis acid" refers to a substance that acts as a Lewis acid with respect to the source of the radical.

The source of the radical is not particularly limited, but when the radical is a chlorine dioxide radical, for example, chlorous acid (HClO ₂ ) or a salt thereof can be mentioned. The salt of chlorous acid is not particularly limited, and examples thereof include metal salts. Examples of the metal salt include alkali metal salts, alkaline earth metal salts, rare earth salts and the like.

More specifically, the sources of the chlorine dioxide radicals include, for example, sodium chlorite (NaClO ₂ ), lithium chlorite (LiClO ₂ ), potassium chlorite (KClO ₂ ), and magnesium chlorite (KClO 2). Examples include Mg (ClO ₂ ) ₂ ) and calcium chlorite (Ca (ClO ₂ ) ₂ ). These chlorous acids and salts thereof may be used alone or in combination of two or more. Among these, sodium chlorite is preferable from the viewpoint of cost, ease of handling, and the like.

The concentration of the radical source in the aqueous phase and / or the organic phase is not particularly limited, but is, for example, 0.0001 mol / L or more, and for example, 1 mol / L or less.
The Lewis acid may be, for example, an organic substance or an inorganic substance.

Examples of the organic substance include ammonium ions and organic acids (for example, carboxylic acids).
The inorganic substance may contain one or both of metal ions and non-metal ions. The metal ion may contain one or both of a typical metal ion and a transition metal ion.

The inorganic substances include, for example, alkaline earth metal ions (for example, Ca ²⁺ ), rare earth ions, Mg ²⁺ , Sc ³⁺ , Li ⁺ , Fe ²⁺ , Fe ³⁺ , Al ³⁺ , silicate ions, and the like. And at least one selected from the group consisting of borate ions.

Examples of the alkaline earth metal ion include calcium, strontium, barium, or radium ions, and more specifically, for example, Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , and Ra ²⁺ . Can be mentioned.

The rare earth is a general term for a total of 17 elements, including two elements of scandium ₂₁ Sc and yttrium ₃₉ Y, and 15 elements (lantanoids) from lanthanum ₅₇ La to lutetium ₇₁ Lu. Examples of the rare earth ion include trivalent cations for each of the 17 elements.

When the Lewis acid is an ion, the Lewis acid may be a substance having a counter ion of the ion, and the counter ion may be, for example, a trifluoromethanesulfonic acid ion (CF ₃ SO ₃ ⁻ , Or ^OTf- ), trifluoroacetate ion (CF ₃ ^COO- ), acetate ion, fluoride ion, chloride ion, bromide ion, iodide ion, sulfate ion, hydrogen sulfate ion, sulfite ion, nitrate ion, Examples thereof include nitrite ion, phosphate ion and phosphite ion. The Lewis acid may be, for example, scandium triflate (Sc (OTf) ₃ ).

The Lewis acid (including counter ions) is selected from the group consisting of, for example, AlCl ₃ , AlMeCl ₂ , AlMe ₂ Cl, BF ₃ , BPh ₃ , BMe ₃ , TiCl ₄ , SiC ₄ , and SiCl ₄ . There may be at least one. However, "Ph" represents a phenyl group and "Me" represents a methyl group.

The Lewis acidity of the Lewis acid is, for example, 0.4 eV or more, but is not limited thereto. The upper limit of the Lewis acidity is not particularly limited, but is, for example, 20 eV or less. The Lewis acidity is, for example, Ohkubo, K .; Fukuzumi, S. Chem. Eur. J., 2000, 6, 4532, J. AM. CHEM. SOC. 2002, 124, 10270-10271, or J. It can be measured by the method described in. Org. Chem. 2003, 68, 4720-4726.

The Bronsted acid is not particularly limited, but may be, for example, an inorganic acid or an organic acid, for example, trifluoromethanesulfonic acid, trifluoroacetic acid, acetic acid, hydrofluoric acid, hydrochloride, hydrobromic acid, iodine. Examples thereof include hydrohydrogenic acid, sulfuric acid, sulfite, nitrate, nitrite, phosphoric acid and phosphite.

The acid dissociation constant _pKa of the Bronsted acid is, for example, 10 or less. The lower limit of pK _a is not particularly limited, but is, for example, -10 or more.
The concentration of at least one of the Lewis acid and Bronsted acid in the aqueous phase and / or the organic phase is not particularly limited and can be appropriately set, but may be, for example, 1 mg / L or more, 1 g. It may be less than / L.

For the oxygen (O ₂ ), for example, air or in at least one of the water and organic phases before or after adding the radical source, the Lewis acid, the Bronsted acid, the molding substrate and the like. Oxygen may be dissolved by blowing oxygen gas. At this time, for example, the water may be saturated with oxygen (O ₂ ). When at least one of the aqueous phase and the organic phase contains the oxygen (O ₂ ), for example, the oxidation reaction of the olefin polymer constituting the molding base material can be further promoted.

<Radical generation process>
The production method of the present invention may include a step of generating the radical (radical generation step), specifically, a step of generating the radical from the radical generation source.

The radical generation step is not particularly limited, but is performed, for example, by dissolving the radical source (for example, chlorous acid or a salt thereof) in water and allowing it to stand, and spontaneously generating the radical from the radical source. be able to. At this time, for example, the presence of at least one of the Lewis acid and the Bronsted acid in the water further promotes the generation of the radical. Further, for example, the radical may be generated by irradiating the aqueous phase in which the radical generation source is dissolved in water with light. This light irradiation may be the light irradiation in the step 1, that is, the radical may be irradiated with the light in the step 1 while generating the radical.

For example, the mechanism by which chlorine dioxide radicals are generated from chlorite ions is presumed as in Scheme 1 below. However, Scheme 1 below is an example of a presumed mechanism and does not limit the present invention in any way.

The first reaction formula (upper) of Scheme 1 below shows the disproportionation reaction of chlorite ion (ClO _2- ⁾ , and at least one of Lewis acid and Bronsted acid is present in this reaction system. Therefore, it is considered that the equilibrium tends to move to the right side.

The second (middle) reaction formula in Scheme 1 below shows a dimerization reaction, and the hypochlorite ion ( ^ClO- ) generated by the disproportionation reaction reacts with the chlorite ion to form dicarbonate. Chlorine (Cl ₂ O ₂ ) is produced. It is considered that this reaction is more likely to proceed as the amount of proton H ⁺ in the water increases, that is, the more acidic it is.

The third (lower) reaction equation in Scheme 1 below represents radical generation. In this reaction, dichlorine dioxide produced by the second reaction formula reacts with chlorite ions to generate chlorine dioxide radicals.

In the step 1, the wavelength of the irradiation light may be appropriately selected so that the molding base material can be modified according to the radicals used. Specifically, a wide range from the infrared region to the ultraviolet region can be selected, and for example, it may be 200 nm or more, or 800 nm or less. The light irradiation time is not particularly limited, but may be, for example, 1 minute or more, or 1000 hours or less.

The temperature at which the step 1 is performed is not particularly limited, but may be, for example, 0 ° C. or higher, or 100 ° C. or lower.
The atmospheric pressure at the time of performing the step 1 is not particularly limited, but may be, for example, 0.1 MPa or more, or 100 MPa or less.

The step 1 may be performed at normal temperature (eg, 5 to 35 ° C.) and normal pressure (atmospheric pressure) without heating, pressurizing, depressurizing, or the like, as shown in Examples described later. It is possible. Further, in the production method of the present invention, for example, as shown in Examples described later, it is also possible to perform the step 1 or all the steps including the above step 1 in the atmosphere without performing the inert gas substitution or the like. Is.

In the light irradiation, the light source is not particularly limited, and examples thereof include visible light contained in natural light such as sunlight. Further, for example, instead of or in addition to the natural light, a light source such as a xenon lamp, a halogen lamp, a fluorescent lamp, or a mercury lamp may or may not be used as appropriate. Further, a filter that cuts wavelengths other than the required wavelength may or may not be used as appropriate.

Further, in the present invention, the molding type base material contains an olefin polymer, and the olefin polymer has a structure having a carbon-hydrocarbon single bond like ethane and the like. It can be inferred that the reaction proceeds by a mechanism similar to the mechanism in which ethanol is produced by the described ethane oxidation reaction. Moreover, since the reaction used in the present invention proceeds via light, a region exposed to light in the presence of the radical, that is, a region mainly on the surface of the molding base material that comes into contact with the phase containing the radical. Is expected to react mainly. By utilizing this property, even if the olefin polymer molecules constituting the molding base material are cleaved or crosslinked by the modification reaction, they remain near the surface of the molding mold, and the strength of the molding mold, etc. Since there is a possibility that the influence on the internal performance of the molding die related to the performance of the molding die can be minimized, it is advantageous in maintaining the strength of the molding die.

The surface refers to a region from the surface of the molding mold to a depth of 1/10 or less, more preferably 1/20 or less of the thickness in the shape. The depth of this denatured portion can be confirmed, for example, by the XPS method.

Further, by using a photomask, it is possible to modify only a specific region of the molding mold base material, and it is also possible to freely control the ratio of the modified region to the unmodified region in the molding mold. Is expected.

For example, in the molding mold of the present invention, the area of the portion to be modified may be appropriately selected according to the desired use of the obtained molding mold, with the entire surface through which light is transmitted as 100%. The preferred lower limit of the area ratio is preferably 1%, 5%, 10%, 20%, 30%, and 50%, and the preferred upper limit is 100%, more preferably 90%. The denatured region can be identified by a known method such as the XPS method.

It is considered that the denaturation proceeds from the radical of the group 17 element generated by irradiating the radical with light. Therefore, it is considered that the modification occurs at the portion where the radical comes into contact with the molding base material to be modified. Therefore, in the case of the above method, the area irradiated with light on the molding base material to be modified and the modified area may be considered to be substantially equivalent.

The peripheral part irradiated with light and the deep part of the pores that the light does not reach may be denatured, but the ratio is considered to be small.
In the present invention, irradiating the molding base material with light may not directly relate to the modification reaction to the molding mold base material. However, considering the life of general radicals and the case of denaturing a molding mold base material to a specific site, it is preferable to substantially irradiate the molding mold base material with light.

Further, when the production method of the present invention is used, the present invention is not limited to the hydroxy group, carboxy group, aldehyde group, carbonyl group, ether bond, ester bond, —C (= O) OOH, —O—O— and the like. Group elements, typically chlorine, may also be introduced into the olefin polymer constituting the molding base material at the same time. Of course, by changing the type of radical used, it is possible to introduce not only chlorine but also bromine and iodine. When a low-molecular-weight hydrocarbon compound such as alkane is used as a substrate, it has been reported that the introduction of chlorine is suppressed by the method using a chlorine dioxide radical as in the present invention. When a material is used, an atom (β) of a group 17 element such as chlorine may be introduced together with an atom (α) of an element selected from group 15 and 16 elements such as oxygen. It is considered that the abundance density of carbon-hydrogen bonds in the olefin polymer tends to be higher than that in the case of using a small molecule such as methane or ethane as a substrate, and it has an interaction with the polymer. The present inventors consider that the possibility of stabilizing radicals may be one of the causes. However, this conjecture does not limit the invention.

The lower limit of the ratio of the total amount of atoms (α) [Cα] to the total amount of atoms (β) [Cβ] introduced into the molding base material (that is, [Cα] / [Cβ]). Is preferably more than zero, more preferably 0.01, still more preferably 0.1, particularly preferably 0.5, and the upper limit is preferably 5000, more preferably 100, still more preferably 20. ..

The above-mentioned [Cα] and [Cβ] values are values specified by the XPS method. In the present invention, the measurement is carried out by a conventional method using the product name AXIS-Nova (manufactured by KRATOS) or an equivalent device thereof.

Further, after the step 1 of irradiating with light, the molding die may be washed several times and then dried, if necessary.
According to the present invention, for example, an olefin polymer that generates a chlorine atomic radical Cl and an oxygen molecule O ₂ by simply irradiating an aqueous solution of chlorine dioxide radicals with light to form a molding base material. An oxidation reaction can be carried out. Then, by such a simple method, it is possible to efficiently modify the molding base material containing the olefin polymer to manufacture the molding mold even under extremely mild conditions such as normal temperature and normal pressure. Is.

Further, according to the present invention, for example, the olefin polymer constituting the molding base material is oxidized without using a radical generator such as a peroxide or an azo compound which may be unstable at the handling temperature. You can also do it. According to this, in addition to being able to carry out the reaction under extremely mild conditions such as normal temperature and pressure as described above, it is possible to efficiently produce a molding base material modified in a highly safe environment, that is, a molding mold. It is also possible to obtain.

The introduced functional groups such as the substituent containing oxygen can further enhance the function of the molding mold or change the properties by reacting with other components. For example, by using the functional group as a scaffold and reacting it with a silicone component having various structures, it is possible to impart extremely high releasability to the molding mold. As a suitable example, if the surface of a molding base material made of a fluorine-containing ring-opening metathesis polymer is oxidized and then reacted with a silicone component, the molding mold is imparted with extremely high releasability. Is possible. In the case of the above application, the effect of introducing the group 17 element at the same time as the above-mentioned oxidation may not always be effective.

The molding mold produced by the method of the present invention is expected to be useful for providing a molded product used for various purposes. For example, when used for the nanoimprint film, it may be necessary to have a higher releasability than before in order to stably realize a more complicated and minute shape than before. It is expected that the technique of the present invention is suitable for realizing such a shape. Specifically, for example, according to the manufacturing method of the present invention, even in the case of manufacturing a nanoimprint molding mold having a complicated and minute pattern shape, it can be expected that the details can be modified. This is because it is presumed that a reaction starting from a radical having a simple structure such as a chlorine radical occurs in the step 1 as in the estimation mechanism, and the high motility of the radical can be expected. ..

Further, after the modification such as oxidation is performed by the above-mentioned production method of the present invention, the silicone component can be further introduced using the functional group introduced into the olefin polymer constituting the molding mold as a scaffold.

In the case of mandrel applications, it can be expected that the range of applicable resins will be expanded. More specifically, it is expected that resin molding dies, which were difficult to use in the past due to their easy stickiness, can be overcome by improving the releasability by using the same technique as described above. ..

In addition, since it is possible to modify only the necessary parts, it can be expected that the strength and durability of the molding mold will not significantly impair the potential of the olefin polymer as a raw material.

Hereinafter, examples of the present invention will be described. However, the present invention is not limited to the following examples.
[Examples 1 and 2]
(Manufacturing of nanoimprint molding molds)
In a circular chalet with a diameter of about 9 cm, the amounts of sodium chlorite (manufactured by Sigma-Aldrich) and 45 mL of ultrapure water shown in Table 1 were placed, and 35 after the sodium chlorite was dissolved in the ultrapure water. 60 μL of a 37% aqueous hydrochloric acid solution (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added. It was confirmed in advance by the ESR method that chlorine dioxide radicals were generated under these conditions. Next, the petri dish containing the obtained mixed solution was subjected to the following formula having a size of about 10 cm × 10 cm × 50 μm.

で表される構造単位を有するフッ素含有オレフィンポリマー（ＦＲＯＭＰ（登録商標）、三井化学（株）製）シートで密封した。なお、前記シートは前記混合液の液面には接触せず、反応は気相環境で行われた。前記のラジカルを含む液面とシートとの距離は、約２センチメートルとした。（ＦＲＯＭＰ（登録商標）のガラス転移温度（前記の示差走査熱量計を用いて、最初の昇温時の測定結果で決定）は１０７℃であった。）
次いで、シートで密封したシャーレの上からパイフォトニクス（株）製ホロライト・カク ＤＣ１２Ｖで、表１に記載された所定の時間、照度１４ｍＷ／ｃｍ²、波長３６５ｎｍの光を照射した。その後、シートを剥がし、シート表面全体を洗瓶で超純水をかけて洗浄し、次いでシートを減圧乾燥し、シート（以下「酸化シート」とも記載する。）を得た。前記フッ素含有オレフィンポリマーシートが、混合液と向き合う側の表面に微細パターンが形成されたもの（すなわち、ナノインプリント成形用型基材）であれば、得られる酸化シートは、ナノインプリント成形用型として好適であると言える。

It was sealed with a fluorine-containing olefin polymer (FORMP®, manufactured by Mitsui Chemicals, Inc.) sheet having a structural unit represented by. The sheet did not come into contact with the liquid surface of the mixed solution, and the reaction was carried out in a vapor phase environment. The distance between the liquid surface containing the radical and the sheet was about 2 cm. (The glass transition temperature of FROMP (registered trademark) (determined by the measurement result at the time of the first temperature rise using the above-mentioned differential scanning calorimeter) was 107 ° C.).
Next, a petri dish sealed with a sheet was irradiated with light having a illuminance of 14 mW / cm ² and a wavelength of 365 nm for a predetermined time shown in Table 1 with Holorite Kaku DC12V manufactured by Piphotonics Co., Ltd. Then, the sheet was peeled off, the entire surface of the sheet was washed with ultrapure water in a washing bottle, and then the sheet was dried under reduced pressure to obtain a sheet (hereinafter, also referred to as "oxidized sheet"). If the fluorine-containing olefin polymer sheet has a fine pattern formed on the surface facing the mixed liquid (that is, a nanoimprint molding mold base material), the obtained oxide sheet is suitable as a nanoimprint molding mold. It can be said that there is.

[Comparative Example 1]
A fluorine-containing olefin polymer (FORMP®, manufactured by Mitsui Chemicals, Inc.) sheet having a size of about 8 cm × 8 cm × 50 μm was prepared, and no modification treatment was performed on this sheet.

[Comparative Examples 2 to 4]
(UV ozone treatment of fluorine-containing olefin polymer sheet)
Using a UV ozone cleaning device (manufactured by Iwasaki Electric Co., Ltd.) on a fluorine-containing olefin polymer (FORMP, manufactured by Mitsui Kagaku Co., Ltd.) with a size of approximately 8 cm x 8 cm x 50 μm, the temperature is 25 ° C and the humidity is 54%. Under the environmental conditions of, UV was irradiated for 5 minutes at a light source output of 20 W (low pressure mercury lamp, λ = 254 nm) (UV ozone treatment was carried out).

[Comparative Example 3]
UV ozone treatment was carried out in the same manner as in Comparative Example 2 except that the UV irradiation time was changed to 15 minutes.

[Comparative Example 4]
UV ozone treatment was carried out in the same manner as in Comparative Example 2 except that the UV irradiation time was changed to 30 minutes.

(Evaluation of hydrophilicity)
Using the solid surface energy analyzer CA-XE type (manufactured by Kyowa Interface Science Co., Ltd.), water contact between the front surface and the back surface of the sheet obtained in Examples and the like under environmental conditions of a temperature of 23 ° C. and a humidity of 54%. The angle was measured with a water droplet volume of 0.6 μL. The measurement results are shown in Table 2. In Examples 1 and 2, the surface of the sheet facing the mixed liquid side when the petri dish is sealed is defined as the front surface, and the opposite surface is defined as the back surface. In Comparative Examples 2 to 4, the surface of the sheet is defined. Of these, the surface facing the UV light source side during UV ozone treatment was defined as the front surface, and the opposite surface was defined as the back surface. In Examples 1 and 2, the water contact angle of the region of the surface of the sheet that was in contact with the gas phase in the petri dish was measured.

From the comparison with the water contact angle result of Comparative Example 1, in Comparative Examples 2 to 4, the water contact angle was lowered on both the front surface and the back surface of the fluorine-containing olefin polymer sheet, which suggests that the fluorine-containing olefin polymer sheet was hydrophilized. .. On the other hand, in Examples 1 and 2, the decrease in the water contact angle on the front surface is large and the difference in the water contact angle on the back surface is small, suggesting that the front surface has been hydrophilized. That is, according to Examples 1 and 2, it is possible to manufacture a nanoimprint molding mold having one surface hydrophilized.

<Evaluation of appearance and strength of molding mold>
The appearance of the oxidized sheet was visually evaluated, and the strength was evaluated from the tensile feeling. Further, as a comparative example, the appearance of the untreated sheet was visually evaluated, and the strength was evaluated from the tensile feeling.
The details of the evaluation criteria are as follows.
"exterior"
◯: There is no visual difference such as yellowing or white spots based on the sheet of Comparative Example 1.
X: Yellowing and white spots are visually recognized with reference to the sheet of Comparative Example 1.
"Strength"
◯: The strength when pulled by hand is equal to or higher than the sheet of Comparative Example 1. ×: The strength when pulled by hand is clearly reduced based on the sheet of Comparative Example 1.

Claims (6)

Atoms (α) of elements selected from Group 15 and Group 16 elements and atoms (β) of Group 17 elements in one molecule are atomized in atomic number ratio: atom (α): atom (β) = 1: 1 ~ 1. The step 1 of irradiating a radical contained in a ratio of 4: 1 with light is included.
A method for producing a molding mold, which comprises modifying a molding base material containing an olefin polymer having a melting point and / or a glass transition temperature of 70 ° C. or higher and 300 ° C. or lower.
The step 1 is
In an environment where the molding base material and the radical coexist
This is a step of irradiating the radical with light to denature the molding base material.
Manufacturing method of molding mold. The method for manufacturing a molding mold according to claim 1 , wherein the step 1 is a step of irradiating the molding base material and the radical with light. The method for manufacturing a molding die according to claim 1 or 2 , wherein a part of the molding die is in an unmodified state. The method for producing a molding mold according to any one of claims 1 to 3 , wherein the olefin polymer is a fluorine-containing olefin polymer. The method for producing a molding mold according to any one of claims 1 to 4 , wherein the radical is a chlorine dioxide radical. The method for manufacturing a molding mold according to any one of claims 1 to 5 , wherein the molding mold is a mold for nanoimprint molding.

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