JP2016131718A - Manufacturing method of insole and insole - Google Patents

Abstract

PROBLEM TO BE SOLVED: To quickly manufacture an insole by a simple method that is formed to the shape of a sole, is flexible and excellent in elongation and followability to a sole.SOLUTION: There is provided a method for manufacturing an insole formed to the shape of a sole of a human body by previously encapsulating photocurable resin composition (B) in a member including soft film (A), forming the shape that follows the sole by pressing the sole against the soft film, and curing the photocurable resin composition (B) by irradiating light to it. The photocurable resin composition (B) includes photocurable resin (I) which includes, on an average, 0.9-2.5 photocrosslinkable groups in one molecule and a photoinitiator (II).SELECTED DRAWING: None

Description

  The present invention relates to an insole manufacturing method and an insole. More specifically, the photocurable resin composition (B) is encapsulated in a member including the soft film (A) in advance, and a shape following the sole is formed by pressing the sole against the soft film, and light is emitted. The present invention relates to a method and an insole for producing an insole shaped into the shape of a sole of a human body by irradiating and curing the photocurable resin composition (B).

  When wearing shoes, it is common to use an insole (shoe insole). The insole is used for the purpose of deodorizing or ensuring air permeability, etc. It has been. In particular, sports shoes are sold with an insole attached in advance in order to relieve the load on the soles and to reduce the impact during walking and exercise. On the other hand, women's shoes and men's shoes are rarely sold with the insole attached in advance, and each individual purchases and installs a commercially available insole in consideration of size, shape, hardness, effect, etc. Is common.

  However, since the soles of individuals are infinitely different and existing commercial insoles may not match the shape of each individual's soles, it may cause problems such as difficulty in walking and hurting the feet. There is. It is known that when the insole is molded according to the shape of the foot, the load is distributed over the entire sole, making it hard to get tired or causing pain, but it matches the individual foot by applying conventional shoe manufacturing methods If an insole is made, each person's foot shape is required, which takes a lot of time, effort and cost. In addition, conventional insole materials each require heating for curing and molding, or a mold or the like is required to obtain the desired shape, so the material providing method was previously molded into a certain shape It is common to have a shape that is supplied, or a shape that is supplied in sheet form by cutting or punching, etc., or a combination of these members to form a shape similar to the sole shape It is. In these methods, it is necessary to produce a die or a punching blade for each desired shape, which is disadvantageous economically and requires time for production. It was difficult to obtain easily and quickly.

  In order to solve these problems, for example, in Patent Document 1, a sole mold is formed on a polymer viscoelastic body, a liquid curable resin is poured into the mold, and a second mold is manufactured. A method of manufacturing an insole that matches the shape of each individual's foot by manufacturing an insole adapted to the two molds is disclosed.

  In Patent Document 2, a pad included in a state where a two-component curable resin is separated in advance is used, both are mixed in the pad, pressed against a human body or an object while being reaction-cured, and deformed and held according to the shape. A support pad is disclosed.

  Similarly, Patent Document 3 discloses a method for manufacturing an insole of an arch by enclosing a two-component mixed silicone resin in a flexible sheet material.

  Patent Document 4 discloses a method of manufacturing an insole that covers a silicone resin with a wrap film, and is cured by placing a foot on the silicone resin to fit the sole.

  Patent Document 5 discloses a cast that encloses a curing raw material in a connected bag body and cures it according to a desired portion. As an example of usage, an ultraviolet curable acrylic resin is injected into the curing raw material, A method is described in which the body is pressed against the body and irradiated with ultraviolet rays to form a desired shape.

  Patent Document 6 discloses a method for producing a gel mat in which a water-based UV curable resin is cured in a gel bag.

JP-A-7-314582 JP 2007-260189 A JP 2011-19788 A JP 2005-198921 A Japanese Patent Laid-Open No. 9-241953 JP2012-210408A

  The method of Patent Document 1 is cumbersome, and therefore requires a lot of cost, time, and labor, and has low practicality.

  In the method of Patent Document 2, there is a case where the mixing is insufficient and does not sufficiently cure, and if the curing after mixing is early, the curing occurs while considering an appropriate position. It is necessary to press the curing pad for a long time, and the person who is pressed feels pain that it is necessary to continue the same posture for a long time, or the position shifts before curing and it can not form an appropriate shape There was a bug.

  Even in the method of Patent Document 3, when a reaction-curing type is used as described above, there are always problems such as problems related to curing time and poor mixing, as described above.

  According to the method of Patent Document 4, it may be necessary to wait for a long time until the silicone resin is cured, or sufficient flexibility and strength may not be obtained depending on the silicone resin, which may cause back pain.

  In the method of patent document 5, since the bag body for enclosing an acrylic resin has a complicated structure, it is economically disadvantageous. Moreover, it is not described what is suitable as such an ultraviolet curable acrylic resin, and conventionally known ultraviolet curable acrylic resins generate a large amount of heat (curing heat) during curing. Therefore, there is a possibility that burns may occur with curing when actually in contact with the human body, and the cured resin is generally very hard, even if it can be used for gibbs, It is difficult to use as an insole for shoes used for exercise. In addition, the ultraviolet curable acrylic resin described can not be produced with a thickness of 2 mm or more because of uneven curing, but a space of 2 mm or more may be formed in the arch between the sole of the human body and the shoe sole. Since it is common, it has been difficult to apply such a method to an insole.

  According to the method of Patent Document 6, it is possible to manufacture a gel mat having a fixed shape, but it is impossible to manufacture gel mats having various shapes and those following the body shape of each individual.

  As described above, in the conventional method, it is difficult to obtain an insole in which the shape following the sole is simply formed into a bowl shape, and the cured product is hard even when the cured product is obtained using an ultraviolet curable resin. For this reason, it is difficult to produce an insole that is flexible and does not interfere with walking or movement, but has excellent tracking performance and shock-absorbing properties. It was also difficult to obtain such an insole.

  An object of this invention is to manufacture the insole shape | molded in the shape which followed the sole.

  In view of the above circumstances, as a result of intensive studies on the method of forming a shape that follows the sole of the foot, the present inventors have found that the above-mentioned problems can be solved, and have obtained the present invention.

  That is, in the present invention, the photocurable resin composition (B) is encapsulated in a member containing the soft film (A) in advance, and the photocurable resin composition is irradiated with light while the soft film is pressed against the sole. A method for producing an insole shaped into a sole shape by curing a product (B), wherein the photocurable resin composition (B) averages photocrosslinkable groups in one molecule. The present invention relates to a method for producing an insole comprising 0.9 to 2.5 photocurable resins (I) and a photoinitiator (II).

  As a preferred embodiment, the present invention relates to a method for producing an insole, wherein the member is a composite member of a flexible film (A) and another member (C).

  As a preferred embodiment, the present invention relates to a method for producing an insole, wherein the hardness of the photocurable resin composition (B) after curing is E80 or less with a type E hardness meter.

  In a preferred embodiment, the insole is characterized in that the soft film (A) is one using a soft material selected from polyvinyl chloride, polyolefin, polyurethane, and ethylene / vinyl acetate copolymer. It relates to the manufacturing method.

  In a preferred embodiment, the photocurable resin (I) is any one selected from urethane (meth) acrylate, epoxy (meth) acrylate, ester (meth) acrylate, silicone (meth) acrylate, and acrylic (meth) acrylate. It is related with the manufacturing method of the insole characterized by being one or more photocurable resin.

As a preferred embodiment, the photocrosslinkable group of the photocurable resin (I) has the general formula (1):
—OC (O) C (R ¹ ) ═CH ₂ (1)
(In the formula, R ¹ represents a hydrogen atom or an organic group having 1 to 20 carbon atoms).

  As a preferred embodiment, the present invention relates to a method for producing an insole, wherein the photocurable resin (I) has at least 0.8 photocrosslinkable groups at the molecular chain terminals.

  As a preferred embodiment, the present invention relates to a method for producing an insole, wherein the photocurable resin (I) has a molecular weight of 1,000 or more.

  As a preferred embodiment, the present invention relates to a method for producing an insole, wherein the photocurable resin (I) is a (meth) acrylic polymer synthesized by a living radical polymerization method.

  As a preferred embodiment, the present invention relates to a method for producing an insole, wherein the photoinitiator (II) is 0.01 to 10 parts by weight with respect to 100 parts by weight of the photocurable resin (I).

  As a preferred embodiment, the present invention relates to a method for producing an insole, wherein the irradiated light is light having a peak illuminance at a wavelength of 350 nm or more.

  As a preferred embodiment, the present invention relates to a method for manufacturing an insole, wherein the light source to be irradiated is LED light having a peak illuminance at a wavelength of 400 nm or more.

As a preferred embodiment, the present invention relates to a method for producing an insole, wherein a peak illuminance of irradiated light is 20 mW / cm ² or less.

  The present invention also relates to an insole obtained by any of the production methods described above.

  According to the present invention, it is possible to quickly obtain an insole which is formed into a sole shape, is flexible and excellent in elongation, and has excellent followability to the sole by a simple method.

  Below, it explains in full detail about the component contained in this invention.

  In the present invention, a photocurable resin composition (B) is encapsulated in advance in a member containing a soft film (A), and light is irradiated in a state where the soft film is pressed against the sole of the foot. A method for producing an insole shaped into the shape of a sole by curing (B), wherein the photocurable resin composition (B) has an average of 0 photocrosslinkable groups in one molecule. It is a manufacturing method of the insole characterized by including the photocurable resin (I) which has .9-2.5 pieces, and photoinitiator (II).

<Soft film (A)>
The soft film (A) used in the present invention is not particularly limited, and a general soft film can be used. A soft film is a film made of a material that is flexible and easily stretched, and can follow its shape when it comes into contact with the sole. Specific examples include polyvinyl chloride, polyvinylidene chloride, polyethylene, propylene-based soft polypropylene, ethylene / α-olefin copolymers, ethylene / vinyl acetate copolymers, and ethylene copolymers such as ionomers. And a flexible film made of polyurethane, nylon, or thermoplastic elastomer. Among these, any one flexible film selected from polyvinyl chloride, polyolefin, polyurethane, and ethylene / vinyl acetate copolymer is preferable because of its excellent availability, good touch, and excellent durability. Among them, a polyurethane soft film is most preferable because of excellent workability and good followability to elongation when an insole is used. These flexible films may have a single layer structure made of only one kind of resin, or may use a film material having a multilayer structure.

<Photocurable resin composition (B)>
The photocurable resin composition (B) used in the present invention comprises a photocurable resin (I) having an average of 0.9 to 2.5 photocrosslinkable groups in one molecule and a photoinitiator ( If it consists of II), it will not specifically limit.

<Photocurable resin (I)>
The photocurable resin (I) having 0.9 to 2.5 photocrosslinkable groups on average in one molecule constituting the photocurable resin composition (B) of the present invention is a cured product obtained. If it is flexible and can follow the movement at the time of walking and exercise, it can be used without any particular limitation.

  Photopolymerizable resin having an epoxy group, oxetane group, vinyl ether group or the like as a photocrosslinkable group, or radical polymerization having a polymerizable carbon-carbon double bond such as a (meth) acryloyl group, a vinyl group or an allyl ether group Examples include, but are not limited to, mold resins.

Among these, from the viewpoint of high photoreactivity and versatility, the photocrosslinkable group possessed by the photocurable resin (I) is represented by the general formula (1):
—OC (O) C (R ¹ ) ═CH ₂ (1)
(In the formula, R ¹ represents an organic group of a hydrogen atom or 1 to 20 carbon atoms) is preferably a (meth) acryloyl group represented by, R ¹ since it is rich in easily, also photoreactive obtain the It is preferably a hydrogen atom or a CH ₃ group.

  These photocurable resins are required to have an average of 0.9 to 2.5 photocrosslinkable groups in one molecule. If the number of photocrosslinkable groups is less than 0.9, the strength of the resulting cured product is weak, and sufficient shock-absorbing performance may not be exhibited, and problems such as gradual deformation during use may occur. When there are more than 2.5 photocrosslinkable groups, the resulting cured product is poorly stretched, resulting in an insufficient follow-up operation. More preferably, it is in the range of 0.9 to 1.9 from the point that the shock-absorbing performance is better, and more preferably in the range of 1.1 to 1.5 because the touched person feels good. preferable.

  Furthermore, it is preferable that at least 0.8 of the photocrosslinkable groups have at the molecular chain end from the viewpoint of being more flexible and having good impact buffering performance.

  The photocurable resin (I) used in the present invention may be any polymer or oligomer having a photocrosslinkable group at the main chain terminal and / or side chain. Polyether (meth) acrylate resin containing (meth) acrylate group at the molecular chain terminal or side chain of the polymer, conjugated diene polymer or hydrogenated product thereof (meth) acryloyl group at the molecular chain terminal or side chain Conjugated diene (meth) acrylate-based resin, urethane polymer molecular chain end or side chain urethane (meth) acrylate resin having (meth) acryloyl group, epoxy resin molecular chain end or side chain (meth) Epoxy (meth) acrylate resin having acryloyl group, (meth) acryloyl group at the end of molecular chain or side chain of polyester polymer Polyester (meth) acrylate resin having a (meth) acryloyl group at the molecular chain terminal or side chain of the silicone (meth) acrylate resin having a (meth) acryloyl group at the molecular chain terminal or side chain of the silicone polymer Examples include (meth) acrylic (meth) acrylate resins, (meth) acrylic vinyl resins having a (meth) acryloyl group at the molecular chain terminal or side chain of a vinyl polymer, but are not limited thereto. Absent.

  Among polymers or oligomers having a photocrosslinkable group at the main chain end and / or side chain, the hardness of the resulting cured product can be easily adjusted, and the urethane (meth) acrylate that is commercially available is excellent in durability. Any one or more photo-curable resins selected from epoxy (meth) acrylate, ester (meth) acrylate, silicone (meth) acrylate, and acrylic (meth) acrylate are preferable, and the resulting cured product is flexible. A (meth) acrylic polymer having a photocrosslinkable group at the molecular end is preferable because of its excellent shock-absorbing performance, and it has a (meth) acryloyl group at the molecular end because it is rich in photoreactivity and can be easily photocured. An acrylic polymer is more preferable.

  There are various methods for producing an acrylic polymer having a (meth) acryloyl group at the molecular end, and radical polymerization is preferred from the viewpoint of versatility of the monomer and ease of control. Controlled radical polymerization is more preferred. This controlled radical polymerization method can be classified into a “chain transfer agent method” and a “living radical polymerization method”. Living radical polymerization is more preferred from the viewpoint of easy control of the molecular weight and molecular weight distribution of the resulting acrylic polymer, and the resulting cured product is excellent in flexibility and elongation, availability of raw materials, functional group to the polymer terminal Atom transfer radical polymerization is particularly preferred because of its ease of introduction. The radical polymerization, controlled radical polymerization, chain transfer agent method, living radical polymerization method, and atom transfer radical polymerization are known polymerization methods. For example, JP-A-2005-232419 and JP-A-2005-234419 The description of 2006-291073 gazette etc. can be referred and Kaneka XMAP made from Kaneka is well known as an example.

  These photo-curing resins (I) preferably have a molecular weight of 1,000 or more from the viewpoint that the obtained cured product has a good balance between flexibility and elongation. A molecular weight of 1,000 to 100,000 is preferable from the viewpoint of superiority, and 3,000 to 20,000 is further preferable from a viewpoint of excellent curability.

  When the molecular weight is less than 1,000, it is difficult to obtain a flexible cured product, the viscosity of the photocurable resin composition is lowered, liquid leakage from the encapsulated material occurs, and relatively photocrosslinking property is obtained. Since the concentration of the group becomes high, the generation of reaction heat at the time of photoreaction increases, and there may be a problem that the human body in contact is burned or that the container to be sealed or the mold to be contacted requires heat resistance.

  The molecular weight of the photocurable resin in the present invention is represented by a number average molecular weight (Mn) measured by gel permeation chromatography (GPC). The GPC measurement in the present invention mainly uses chloroform as a mobile phase, the measurement is performed with a polystyrene gel column, and the number average molecular weight and the like can be determined in terms of polystyrene.

  These photocurable resins may be used alone or in combination with a plurality of resins. When a plurality of resins are mixed and used, the number of photocrosslinkable groups of each resin may be 0.9 to 2.5 on average. The average number of photocrosslinkable groups in the case of mixing is calculated in the same manner as the AFB value (“average functionality of blend”) defined in paragraph [0028] of JP-T-2014-531489. That is, the average number of photocrosslinkable groups = (number of photocrosslinkable groups of resin 1) * (wt% of resin 1 in the mixture) + (number of photocrosslinkable groups of resin 2) * (wt% of resin 2) +. Calculated as + (number of photocrosslinkable groups of resin X) * (wt% of resin X).

<Photoinitiator (II)>
The photoinitiator is not particularly limited as long as it is a compound that is activated by an active energy ray such as UV, visible light, or electron beam and generates a substance necessary for curing the photocurable resin (I). Good. In recent years, since less energy is required for curing and the work environment can be kept good, when the photocrosslinkable group of the photocurable resin (I) is a (meth) acryloyl group, UV, visible light, electron The case where it hardens | cures using the photo radical initiator which a radical generate | occur | produces by active energy rays, such as a line | wire, is easy to be liked. When the photocurable resin (I) is a cationic polymerization type resin having an epoxy group, an oxetane group, a vinyl ether group or the like as a photocrosslinkable group, a general photocation generator may be used.

  The photo radical initiator is not particularly limited. For example, acetophenone, propiophenone, benzophenone, xanthol, fluorin, benzaldehyde, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-methylacetophenone, 3- Pentylacetophenone, 2,2-diethoxyacetophenone, 4-methoxyacetophenone, 3-bromoacetophenone, 4-allylacetophenone, p-diacetylbenzene, 4-methylbenzophenone, 3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone 4,4′-dimethoxybenzophenone, dibenzosuberone, dibenzosuberenone, 4-chloro-4′-benzylbenzophenone, 3-chloroxanthone, 3,9 Dichloroxanthone, 3-chloro-8-nonylxanthone, benzoin, benzoin methyl ether, benzoin butyl ether, bis (4-dimethylaminophenyl) ketone, benzylmethoxy ketal, 2-chlorothioxanthone, 2,2-dimethoxy- 1,2-diphenylethane-1-one (trade name IRGACURE651, manufactured by BASF Japan), 1-hydroxy-cyclohexyl-phenyl-ketone (trade name IRGACURE184, manufactured by BASF Japan), 2-hydroxy-2-methyl-1-phenyl -Propan-1-one (trade name DAROCUR 1173, manufactured by BASF Japan), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (trade name IRGACUR 2959, manufactured by BASF Japan), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name IRGACURE907, manufactured by BASF Japan), 2-benzyl-2-dimethylamino- 1- (4-morpholinophenyl) -butanone-1 (trade name IRGACURE369, manufactured by BASF Japan), 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholin-4-yl-phenyl)- Butan-1-one (trade name IRGACURE 379, manufactured by BASF Japan), dibenzoyl, 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl] -2-methyl- Propan-1-one (trade name IRGACURE127, manufactured by BASF Japan), 1- [4- 4-Benzoxylphenylsulfanyl) phenyl] -2-methyl-2- (4-methylphenylsulfonyl) propan-1-one (trade name ESURE1001M), methylbenzoylformate (trade name SPEEDCURE MBF manufactured by LAMBSON), O-ethoxyimino-1-phenylpropan-1-one (product name: SPEDDCURE PDO LAMBSON), oligo [2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanone (product name: ESCURE KIP150 LAMBERTI 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] 1,2-octanedione (trade name IRGACURE OXE 01, manufactured by BASF Japan), 1- [9-ethyl-6- ( 2-methylbenzoyl)- 9H-carbazol-3-yl] -1- (0-acetyloxime) ethanone (trade name IRGACURE OXE 02, manufactured by BASF Japan), 4-benzoyl-4 ′ methyldiphenyl sulfide, 4-phenylbenzophenone, 4,4 ′, 4 "-(hexamethyltriamino) triphenylmethane, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (trade name DAROCUR TPO, manufactured by BASF Japan), bis (2,4,6-trimethylbenzoyl)- Phenylphosphine oxide (trade name IRGACURE819, manufactured by BASF Japan), bis (2,6-dimethylbenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyl-phenyl-ethoxy- Fo Fin oxide (trade name DAROCUR TPO-L, manufactured by Lambson), an acyl phosphine oxide-based photopolymerization initiators such as trade name Speedcure XKm (manufactured by Lambson). Among these, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name IRGACURE907, manufactured by BASF Japan) having absorption in the long wavelength region, 2-benzyl-2 -Dimethylamino-1- (4-morpholinophenyl) -butanone-1 (trade name IRGACURE369, manufactured by BASF Japan), 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholin-4-yl) -Phenyl) -butan-1-one (trade name IRGACURE 379, manufactured by BASF Japan), 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (trade name DAROCUR TPO, manufactured by BASF Japan), bis (2, 4, 6-trimethylbenzoyl) -phenylphosphine oxide ( Product name IRGACURE 819, manufactured by BASF Japan), bis (2,6-dimethylbenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyl-phenyl-ethoxy-phosphine oxide (trade name) DAROCUR TPO-L, manufactured by LAMBSON), trade name SPEDCURE XKm (manufactured by LAMBSON) 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] 1,2-octanedione (trade name IRGACURE OXE 01, BASF Made in Japan), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (0-acetyloxime) ethanone (trade name IRGACURE OXE 02, manufactured by BASF Japan) Preferred, easy to handle 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (trade name DAROCUR TPO, manufactured by BASF Japan), bis (2,4,6-trimethylbenzoyl) -phenyl Phosphine oxide (trade name IRGACURE 819, manufactured by BASF Japan), bis (2,6-dimethylbenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyl-phenyl-ethoxy-phos Fin oxide (trade name DAROCUR TPO-L, manufactured by LAMBSON) and trade name SPEDCURE XKm (produced by LAMBSON) are preferable, and bis (2,4,6-trimethylbenzoyl) -pheny has good reactivity and excellent deep-curability. Phosphine oxide (trade name IRGACURE819, manufactured by BASF Japan) are most preferred.

  These photo radical initiators may be used alone or in combination of two or more, or may be used in combination with other compounds.

  Specific examples of combinations with other compounds include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, diethanolmethylamine, dimethylethanolamine, triethanolamine, and ethyl. Combinations with amines such as -4-dimethylaminobenzoate and 2-ethylhexyl-4-dimethylaminobenzoate, further combinations with iodonium salts such as diphenyliodonium chloride, combinations with pigments and amines such as methylene blue, etc. Can be mentioned.

  Moreover, in order to improve photoreactivity, you may use combining a general photosensitizer. Although it does not specifically limit as a photosensitizer, For example, anthracene derivative, a benzophenone derivative, a thioxanthone derivative, an anthraquinone derivative, a benzoin derivative etc. are mentioned, More specifically, a 9, 10- dialkoxy anthracene, 2-alkyl thioxanthone, Examples include 2,4-dialkylthioxanthone, 2-alkylanthraquinone, 2,4-dialkylanthraquinone, p, p'-aminobenzophenone, 2-hydroxy-4-alkoxybenzophenone, benzoin ether and the like. More specifically, anthrone, anthracene, 9,10-diphenylanthracene, 9-ethoxyanthracene, pyrene, perylene, coronene, phenanthrene, benzophenone, benzyl, benzoin, methyl 2-benzoylbenzoate, butyl 2-benzoylbenzoate, Benzoin ethyl ether, benzoin-i-butyl ether, 9-fluorenone, acetophenone, p, p'-tetramethyldiaminobenzophenone, p, p'-tetraethylaminobenzophenone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-diethyl Thioxanthone, phenothiazine, acridine orange, benzoflavin, cetoflavin-T, 2-nitrofluorene, 5-nitroacenaphthene, benzoquinone, 2-chloro-4-ni Roaniline, N-acetyl-p-nitroaniline, p-nitroaniline, N-acetyl-4-nitro-1-naphthylamine, picramid, anthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1,2-benzanthraquinone 3-methyl-1,3-diaza-1,9-benzanthrone, dibenzalacetone, 1,2-naphthoquinone, 3,3′-carbonyl-bis (5,7-dimethoxycarbonylcoumarin), 9,10 -Dibutoxyanthracene, 9,10-dipropoxyanthracene, etc. are mentioned. A photosensitizer may be used independently and 2 or more types may be used together.

  In addition, when using the said photoradical initiator, if necessary, hydroquinone, hydroquinone monomethyl ether, benzoquinone, para tertiary butyl techol, 2,2,6,6-tetramethylpiperidine-1-oxyl, N, N- Polymerization inhibitors such as N, N-dialkylhydroxylamine such as diethylhydroxylamine and N, N-distearylhydroxylamine can also be added.

  Although there is no restriction | limiting in particular in the addition amount of a photoradical initiator, 0.01-10 weight part is preferable and obtained with respect to 100 weight part of photocurable resin (I) from the point of sclerosis | hardenability and storage stability. From the point which is excellent in the impact buffering performance of hardened | cured material, 0.1-5 weight part is further more preferable. When the amount is less than 0.01 parts by weight or more than 10 parts by weight, the deep part curability is not sufficiently obtained, and the light irradiation time may take a long time when obtaining a thick film cured product. That is, when the amount is less than 0.01 parts by weight, the radicals necessary for curing the photo-curable resin composition are not sufficiently generated, so that time is required for curing. On the other hand, when it is more than 10 parts by weight, sufficient energy cannot reach the deep part due to excessive absorption of light irradiated by the photoradical initiator present on the irradiation surface side of the photocurable resin composition. It will be inferior to the curability of a deep part.

  <Reactive Diluent> The photocurable resin composition (B) of the present invention includes monomers having a photocrosslinkable group for the purpose of improving workability by reducing viscosity and improving physical properties of the resulting cured product. Can also be used together.

Examples of the photocrosslinkable group include (meth) acryloyl groups such as (meth) acrylic groups, styrene groups, acrylonitrile groups, vinyl ester groups, N-vinylpyrrolidone groups, acrylamide groups, conjugated diene groups, vinyl ketone groups, and chlorides. A vinyl group etc. are mentioned. Among them, the same functional group as the photocrosslinkable group used in the photocurable resin (I) used in the present invention is good, and from the viewpoint of high photoreactivity and versatility, the general formula (1):
—OC (O) C (R ¹ ) ═CH ₂ (1)
(In the formula, R ¹ represents an organic group of a hydrogen atom or 1 to 20 carbon atoms) is preferably a (meth) acryloyl group represented by, R ¹ since it is rich in easily, also photoreactive obtain the It is preferably a hydrogen atom or a CH ₃ group.

  Specific examples of the monomer include (meth) acrylate monomers, styrene monomers, acrylonitrile, vinyl ester monomers, N-vinyl pyrrolidone, acrylamide monomers, conjugated diene monomers, vinyl ketone monomers, vinyl halides and halogenated monomers. Examples include vinylidene monomers and polyfunctional monomers.

  (Meth) acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, (meth ) Isobutyl acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, (meth ) N-octyl acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate , Dodecyl (meth) acrylate, lauryl (meth) acrylate, (meth) acrylic Stearyl acid, isostearyl (meth) acrylate, tridecyl (meth) acrylate, 2-decyltetradecanyl (meth) acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate , 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, (meth ) Glycidyl acrylate, 2-aminoethyl (meth) acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, (meth) 2-Trifluoromethylethyl acrylate, (meth) acrylate 2-perfluoroethylethyl laurate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluoroethyl (meth) acrylate, perfluoromethyl (meth) acrylate, (meth) Diperfluoromethylmethyl acrylate, 2-perfluoromethyl-2-perfluoroethylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, Examples include (meth) acrylic acid 2-perfluorohexadecylethyl.

  Examples of the styrenic monomer include styrene and α-methylstyrene.

  Examples of vinyl ester monomers include vinyl acetate, vinyl propionate, and vinyl butyrate.

  Examples of acrylamide monomers include acrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, acryloylmorpholine, hydroxyethyl acrylamide, isopropyl acrylamide, dimethylaminopropyl acrylamide, diacetone acrylamide, and the like.

  Examples of the conjugated diene monomer include butadiene and isoprene. Examples of the vinyl ketone monomer include methyl vinyl ketone.

  Examples of the vinyl halide / vinylidene halide monomer include vinyl chloride, vinyl bromide, vinyl iodide, vinylidene chloride, and vinylidene bromide.

  Multifunctional monomers include trimethylolpropane triacrylate, neopentyl glycol polypropoxy diacrylate, neopentyl glycol diacrylate, trimethylol propane polyethoxy triacrylate, bisphenol F polyethoxy diacrylate, bisphenol A polyethoxy diacrylate, dipenta Erythritol polyhexanolide hexaacrylate, tris (hydroxyethyl) isocyanurate polyhexanolide triacrylate, tricyclodecane dimethylol diacrylate 2- (2-acryloyloxy-1,1-dimethyl) -5-ethyl-5 -Acryloyloxymethyl-1,3-dioxane, tetrabromobisphenol A diethoxydiacrylate, 4,4-dimercaptodiphenyl Phi blunder methacrylate, polytetramethylene glycol diacrylate, 1,9-nonanediol diacrylate, Cyclohexanedicarboxylic acrylate 1,6, dimethylol tricyclodecane acrylate, ditrimethylolpropane tetraacrylate.

  The addition amount in the case of adding a reactive diluent is not particularly limited, but the workability of the photocurable resin composition (I) is good, the calorific value at the time of curing is small, and the influence on the curing shrinkage rate is small. From the point, 0.1 to 100 parts by weight is preferable and 0.1 to 70 parts by weight is more preferable with respect to 100 parts by weight of the photocurable resin.

<Filler>
A filler can be added to the photocurable resin composition (B) of the present invention as long as the photocurability is not hindered. Specific examples include various fillers and fine hollow particles described in paragraphs [0134] to [0151] of JP-A-2006-291073. As the filler, fine silica that is reinforcing silica such as fumed silica, wet process silica, wood powder, pulp, cotton chips, mica, walnut shell powder, rice husk powder, graphite, white clay, silica (crystalline silica, Fused silica, dolomite, anhydrous silicic acid, hydrous silicic acid, etc.), carbon black, heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, oxidized first Ferrous iron, bengara, aluminum fine powder, flint powder, zinc oxide, activated zinc white, zinc dust, zinc carbonate, shirasu balloon, beads such as polyacrylic resin, polyacrylonitrile-vinylidene chloride resin, phenolic resin, polystyrene resin and the like Hollow fine particles, glass balloon, shirasu balloon, fly-up Inorganic hollow fine particles such as Yubarun, glass fibers, glass filaments, carbon fibers, Kevlar fibers, fibrous fillers such as polyethylene fiber and the like.

  From the point of being excellent in transparency and reinforcement, fumed silica and wet process silica are preferred.

  These may be used alone or in combination of two or more.

  The addition amount in the case of adding a filler is not particularly limited, but 100 parts by weight of the photocurable resin from the viewpoint that the workability of the photocurable resin composition is good and the mechanical properties of the obtained cured product are improved. The amount is preferably 1 to 50 parts by weight, and more preferably 5 to 30 parts by weight.

<Plasticizer>
A plasticizer can be added to the photocurable resin composition (B) of the present invention. By adding a plasticizer, it is possible to adjust mechanical properties such as the viscosity of the photocurable resin composition and the tensile strength, flexibility, and elongation of the resulting cured product, and to improve the transparency of the cured product. Although it does not specifically limit as a plasticizer, According to the objectives, such as adjustment of a physical property and adjustment of properties, phthalic acid esters, such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butyl benzyl phthalate, etc .; Dioctyl adipate , Non-aromatic dibasic acid esters such as dioctyl sebacate, dibutyl sebacate, isodecyl succinate; aliphatic esters such as butyl oleate and methyl acetyl ricinolinate; diethylene glycol dibenzoate, triethylene glycol dibenzoate, penta Esters of polyalkylene glycols such as erythritol esters; Phosphate esters such as tricresyl phosphate and tributyl phosphate; Trimellitic acid esters; Pyromellitic acid esters; Polystyrene Polystyrenes such as poly-α-methylstyrene; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene; chlorinated paraffins; hydrocarbon oils such as alkyldiphenyl and partially hydrogenated terphenyl; process oils; polyethylene Polyether polyols such as glycol, polypropylene glycol, polytetramethylene glycol and the like, and polyethers such as derivatives obtained by converting the hydroxyl groups of these polyether polyols to ester groups, ether groups, etc .; epoxidized soybean oil, epoxy such as epoxy benzyl stearate Plasticizers: dibasic acids such as sebacic acid, adipic acid, azelaic acid, phthalic acid, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene Polyester plasticizers obtained from dihydric alcohols such as Nglycol; Vinyl polymers obtained by polymerizing vinyl monomers such as acrylic plasticizers such as ARUFON series manufactured by Toagosei Co., Ltd. by various methods Etc. These may be used alone or in combination of two or more.

  The addition amount in the case of adding a plasticizer is not particularly limited, but the photocurable resin 100 is preferable because the workability of the photocurable resin composition is good and the effect on the mechanical properties of the resulting cured product is small. The amount is preferably 1 to 200 parts by weight and more preferably 1 to 100 parts by weight with respect to parts by weight.

<Solvent>
A solvent can be mix | blended with the photocurable resin composition (B) used by this invention as needed.

  Solvents that can be blended include, for example, aromatic hydrocarbon solvents such as toluene and xylene; ester solvents such as ethyl acetate, butyl acetate, amyl acetate, and cellosolve; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and diisobutyl ketone Examples of the solvent include alcohol solvents such as methanol, ethanol, and isopropanol; hydrocarbon solvents such as hexane, cyclohexane, methylcyclohexane, heptane, and octane. These may be used alone or in combination of two or more.

  The addition amount in the case of adding a solvent is not particularly limited, but is 100 parts by weight of the photocurable resin from the viewpoint that the workability of the photocurable resin composition is good and the effect on the curing shrinkage due to photocuring is small. The amount is preferably 0.1 to 50 parts by weight, and more preferably 1 to 30 parts by weight.

<Thixotropic agent (anti-sagging agent)>
A thixotropic agent (anti-sagging agent) may be added to the photocurable resin composition (B) of the present invention to impart thixotropy as necessary and improve shape followability.

  The thixotropic inhibitor is not particularly limited, and examples thereof include hydrogenated castor oil derivatives, metal soaps having long-chain alkyl groups, ester compounds having long-chain alkyl groups, inorganic fillers such as silica, amide waxes, and the like. Can be mentioned. These thixotropic agents may be used alone or in combination of two or more.

  The addition amount in the case of adding the thixotropy imparting agent is not particularly limited, but from the point that the workability of the photocurable resin composition is good, 0.1 to 0.1 parts by weight with respect to 100 parts by weight of the photocurable resin. 10 parts by weight is preferable, and 0.1 to 5 parts by weight is more preferable.

<Antioxidant>
An antioxidant (anti-aging agent) can be used in the photocurable resin composition (B) of the present invention. When antioxidant is used, the heat resistance and durability of the cured product obtained can be improved. Antioxidants include general hindered phenolic antioxidants, hindered amine antioxidants (HALS), amine antioxidants, lactone antioxidants, aminoethanol antioxidants and other primary antioxidants. And secondary antioxidants such as sulfur-based oxidants and phosphorus-based oxidants. As the antioxidant, those described in paragraphs [0232] to [0235] of JP-A-2007-308692 and paragraphs [0089] to [0093] of WO05 / 116134 can be used.

  The amount of addition in the case of adding an antioxidant is not particularly limited, but the effect on durability is sufficiently exhibited, and from the viewpoint of not being disadvantageous economically, relative to 100 parts by weight of the photocurable resin. 0.1 to 5 parts by weight is preferable, and 0.1 to 3 parts by weight is more preferable.

<Other additives>
Various additives may be added to the photocurable resin composition (B) of the present invention as necessary for the purpose of adjusting various physical properties of the photocurable resin or the cured product obtained. Examples of such additives include, for example, compatibilizers, curability modifiers, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants, pigments, antifoams. Agents, foaming agents, termite-proofing agents, fungicides, UV absorbers, light stabilizers and the like. Specific examples other than the specific examples of the additives listed in the present specification include, for example, JP-B-4-69659, JP-B-7-108928, JP-A-63-254149, JP-A-62-2904, It is described in Japanese Laid-Open Patent Publication No. 2001-72854.

<Member used for encapsulating the photocurable resin composition (B)>
The photocurable resin composition (B) used in the present invention is a soft film (A) alone or a member composed of the soft film (A) and another member (C), more specifically, in a form enclosed in a container. Provided.

  When the photocurable resin composition is not sealed in a container, not only handling becomes difficult, but also when pressed against the sole, the photocurable resin composition touches the human body and causes chemical burns to the human body. There is a problem that there is a possibility of feeling uncomfortable with the resin touched.

  The container to be sealed may be formed of a soft film alone or may be formed of a soft film and other members, but the portion pressed against the sole needs to be formed of a soft film in order to follow the shape. There is. If the pressed part is not a soft film, it cannot follow the shape and is not suitable for the present invention.

  The other member (C) that forms the composite member with the soft film (A) is not particularly limited as long as it can form an enclosed container together with the soft film (A). The film is preferably made of a hard plastic film or sheet because of its good properties, low cost and excellent workability. A hard plastic is one having a glass transition temperature (Tg) of the resin at room temperature or higher, such as PC, ABS, ABS-PC, vinyl chloride, acrylic resin, PSt, epoxy resin, phenol resin, polyester resin such as PET or PBT, etc. Is mentioned.

  A soft film alone or a container made of a soft film and another member enclosing the photo-curable resin is manufactured by inflation molding, bonding between films, heat fusion, or the like.

  The side of the film or other member forming the container that is irradiated with light must be capable of transmitting the irradiated light so that the internal photocurable resin composition is photocured. That is, when irradiating from the opposite side while pressing against the sole, it is necessary that the opposite side of the portion in contact with the sole is light transmissive. The part in contact with the soles may be transparent or non-transparent, but is more preferably opaque from the viewpoint that the irradiated light is not transmitted and the influence on the soles is small.

  The container to be sealed may be, for example, filled with a photocurable resin composition in a bag formed of a soft film alone or a soft film and another member, and finally the filling port may be bonded or pressure-bonded. The photocurable resin composition may be intentionally protruded from the filling port, and light may be irradiated only to that portion to seal the filling port. In addition, after filling the photocurable resin composition into a flexible film or other member that is preliminarily shaped so that the photocurable resin composition does not spill, the other film or sheet is bonded and bonded or pressure bonded. May be created.

  In addition, the side in contact with the soles has a fabric, natural / artificial leather, deodorization performance and antibacterial performance in order to improve touch and give design and functionality within the range that does not impair the conformity to the shape. The provided fabric or sponge may be bonded together. In any case, it is only necessary to provide the photo-curable resin composition in a container, and it is obvious that the method is not limited to any method.

  The container may cover the entire sole, or may be composed of only necessary portions such as only the heel portion, only the arch portion, or only the vicinity of the mother and child ball portions.

  Moreover, the photocurable resin composition enclosed may be one type, and the 2 or more types of photocurable resin composition may be enclosed. When two or more types of photo-curable resin compositions are encapsulated, the hardness or viscoelastic behavior after curing is different, in that it is easy to impart functionality such as impact buffering and motility. preferable.

<About photocuring method of insole>
The curing method of the photocurable resin composition enclosed in the container is not particularly limited as long as the encapsulated photocurable resin is cured by irradiating some light.

  The light source used for the photocuring of the present invention can be any light source that is used for ordinary photocuring, such as sunlight, low-pressure mercury lamp (sterilizing lamp, fluorescent chemical lamp, black light), cold cathode fluorescent light. Tube (CCFL), fluorescent lamp, incandescent lamp, medium pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, carbon arc lamp, metal halide lamp, gallium lamp, tungsten lamp, xenon lamp, mercury xenon lamp, chemical lamp, electrodeless Examples include a discharge lamp, a zirconium lamp, a field emission lamp, an ultraviolet excimer fluorescent lamp, an organic EL, an LED, and a UV-LED. Among these, high-pressure mercury lamp, metal halide lamp, electrodeless discharge lamp, cold cathode fluorescent tube (CCFL), UV-LED, LED are preferable from the viewpoint of easy handling and economical efficiency, and further irradiation with low illumination is possible. A UV-LED or LED that is easy and can be turned on and off instantaneously is most preferable.

  The wavelength of the light source used for photocuring can be selected as appropriate depending on the irradiation intensity and accumulated light quantity, but it has a peak illumination at a wavelength of 350 nm or more because it has little effect on the human body and little deterioration of the soft film used. LED light having a peak illuminance at a wavelength of 400 nm or more (visible light) is most preferable from the viewpoint that there is less adverse effect on the skin and eyes. These light sources may be used alone or in combination of two or more.

In addition, the irradiation intensity of light and the integrated light quantity are appropriately adjusted according to the type of photo-curable resin, the type and number of photo-initiators, and the thickness and size of the cured product. The peak illuminance of the irradiated light is preferably 100 mW / cm ² or less, more preferably 50 mW / cm ² or less, and adverse effects on the skin and eyes from the viewpoint that there is little impact on the human body when irradiated. Is most preferably 20 mW / cm ² or less.

  A container (hereinafter referred to as a package) in which a photocurable resin composition is enclosed can be formed into a shape that follows the mold of the sole by pressing it against the sole. By irradiating light while maintaining the shape to cure the photocurable resin composition, an insole shaped into a desired shape can be produced.

  For example, on the package using a container manufactured in a shape close to the gap between the sole and the sole in advance, place the foot so that the soft film is on the foot side and follow the shape of the sole, It is possible to produce an insole that follows the shape of the sole of each individual, which has been particularly demanded in recent years, in a short time by irradiating with light and curing while maintaining its shape.

  Since the obtained insole follows the sole shape, the load on the sole is excellent in dispersion, less fatigue, and less pain occurs.

<About the obtained insole>
The hardness after curing of the photocurable resin composition (B) obtained by light irradiation in the present invention is high in impact buffering performance, and the hardness of the cured product from the point that the contact part to the human body is good. Is preferably E80 or less in the type E hardness tester, preferably E50 or less from the viewpoint of better feeling during walking, and more preferably E20 or less because of higher shock absorbing performance. The type E hardness tester is a type E durometer defined in JIS K 6253-3: 2012.

  When there are two or more parts having different hardness in one insole, any one part is preferably E80 or less, and other parts may exceed E80.

<Application>
The insole of the present invention can be used for various insole applications because of its simplicity and feel. As an insole for general consumers, prevention of shoe slippage, hallux valgus, octopus, fish eyes etc. or pain reduction, fatigue reduction, improvement of walking feeling, shock absorption / shock buffering, prevention of pain in soles, insteps, fingers and joints, It is useful for the purpose of preventing knee pain and low back pain, correcting walking posture and standing position, preventing falls, diet, arch correction, and improving sports performance in sports. Furthermore, it is useful for medical insoles, nursing insoles, etc. for the purpose of treatment, correction, rehabilitation, functional assistance, functional recovery, etc. of the elderly, sick and disabled.

  However, it is clear that the insole of the present invention is not limited to the applications described above.

  Specific examples of the present invention will be described below together with comparative examples, but the present invention is not limited to the following examples. “Number average molecular weight” and “molecular weight distribution (ratio of weight average molecular weight to number average molecular weight)” were calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). However, a GPC column filled with polystyrene cross-linked gel (shodex GPC K-804, K-802.5; manufactured by Showa Denko KK) was used as the GPC solvent with chloroform.

The number of functional groups introduced per molecule of polymer was calculated based on the concentration analysis by ¹ H-NMR and the number average molecular weight determined by GPC. NMR was measured at 23 ° C. using Bruker ASX-400 and deuterated chloroform as a solvent.

(Synthesis Example 1) Synthesis example of poly (n-butyl acrylate) polymer [P1] having an acryloyl group According to a known method (for example, described in JP 2012-212216 A), cuprous bromide is a catalyst, Pentamethyldiethylenetriamine as a ligand, diethyl-2,5-dibromoadipate as an initiator, n-butyl acrylate as a monomer, and a ratio of (n-butyl acrylate) / (diethyl-2,5-dibromoadipate) to 160 To obtain terminal bromine group n-butyl polyacrylate.

  This polymer was dissolved in N, N-dimethylacetamide, potassium acrylate was added, and the mixture was heated and stirred at 70 ° C. in a nitrogen atmosphere. N, N-dimethylacetamide in this mixed solution was distilled off under reduced pressure, butyl acetate was added to the residue, and insoluble matter was removed by filtration. The butyl acetate in the filtrate was distilled off under reduced pressure to obtain a poly (n-butyl acrylate) polymer [P1] having acryloyl groups at both ends.

The number average molecular weight of the polymer [P1] was 23,000, the molecular weight distribution was 1.1, and the average number of acryloyl groups introduced per molecule of the polymer was determined by ¹ H-NMR analysis to be about 1.9. It was a piece.

(Synthesis example 2) Synthesis example of poly (n-butyl acrylate) polymer [P2] having an acryloyl group The acryloyl group is formed at both ends in the same manner as in Synthesis example 1 except that the monomer / initiator ratio is 80. A poly (n-butyl acrylate) polymer [P2] was obtained.

The number average molecular weight of the polymer [P2] was 12,000, the molecular weight distribution was 1.2, and the average number of acryloyl groups introduced per molecule of the polymer was determined by ¹ H-NMR analysis to be about 1.8. It was a piece.

(Synthesis example 3) Synthesis example monomer of poly (n-butyl acrylate) / (2-ethylhexyl acrylate) copolymer [P3] having acryloyl group n-butyl acrylate / 2-ethylhexyl acrylate Poly (n-butyl acrylate) / (2-acrylic acid 2-) having acryloyl groups at both ends in the same manner as in Synthesis Example 1, except that 50 parts by weight / 50 parts by weight and the monomer / initiator ratio is 400. Ethylhexyl) copolymer [P3] was obtained.

The number average molecular weight of the polymer [P3] was about 60000, and the molecular weight distribution was 1.4. When the average number of acryloyl groups introduced per molecule of the polymer was determined by ¹ H-NMR analysis, it was about 1.8.

(Synthesis example 4) Synthesis example of poly (n-butyl acrylate) polymer [P4] having an acryloyl group Synthesis example except that α-bromobutyrate is used as an initiator and the monomer / initiator ratio is 80 In the same manner as in Example 1, a poly (n-butyl acrylate) polymer [P4] having an acryloyl group at one end was obtained.

The number average molecular weight of the polymer [P4] was 12,000, the molecular weight distribution was 1.1, and the average number of acryloyl groups introduced per polymer molecule was determined by ¹ H-NMR analysis to be about 0.9. It was a piece.

(Hardness measurement)
The adjusted photocurable resin composition was poured into a container to a thickness of 2 mm and irradiated with light to obtain a rubber-like cured product having a thickness of 2 mm. In accordance with JIS K 6253-3: 2012, three 2 mm-thick test pieces were stacked and measured using a type E durometer. Or after pouring into a container so that it might become thickness of 12 mm, after obtaining the rubber-like hardened | cured material of thickness 12mm, the hardness of the test piece was directly measured using the type E durometer.

(Illuminance measurement)
Peak illuminance and integrated light quantity: The ultraviolet light quantity meter uses EIT's 4-band UV measuring instrument: UV POWER PUCK II, and the measured values were used in a band suitable for the output wavelength of each irradiation device.

<Photoinitiator>
IRGACURE819: bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide DAROCUR1173 manufactured by BASF Japan Ltd. 2-hydroxy-2-methyl-1-phenylpropan-1-one manufactured by BASF Japan <antioxidant>
IRGANOX 1010: Tetrakis- [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane manufactured by BASF Japan.
MARK AO-50: 3,5-di-tbutyl-4-hydroxyphenylpropionic acid octadecyl ester manufactured by ADEKA (Formulation Example 1)
As the photocurable resin, 30 parts by weight of the polymer [P1] obtained in Synthesis Example 1 and 70 parts by weight of the polymer [P4] obtained in Synthesis Example 4 were used (average number of photocrosslinkable groups in one molecule). : 1.2), 0.1 part by weight of IRGANOX1010 (BASF Japan) as an antioxidant and 0.5 part by weight of IRGACURE 819 (manufactured by BASF Japan) as a photoinitiator, After mixing, defoaming was performed to obtain a photocurable resin composition [A1]. The photocurable resin composition [A1] was irradiated with ultraviolet rays at a peak illuminance of 500 mW / cm ² and an integrated light amount of 6000 mJ / cm ² using Heraeus LH-6 (bulb: H-bulb) as an ultraviolet irradiation device. A rubber-like molded body having a thickness of 2 mm was produced. When the hardness was measured, it was E10.

Example 1
A bag-like container produced using a polyurethane elastomer film Higres DU235 (thickness 30 μm) manufactured by Seadom Co., Ltd. as a soft film is filled with the photocurable resin composition [A1] obtained in Formulation Example 1, and a filling port is formed. Heat-sealed. Remove the bottom plate of Kiyohara's Super Resin UV Crystal Lamp 36W (peak illuminance 9 mW / cm ² (365 nm)), place the irradiation device upside down, and place a light-transmitting acrylic plate in the opening on the top surface. It was. The prepared package was placed on an acrylic plate, and a foot was placed on the package to follow the shape of the sole and irradiated with ultraviolet rays for 3 minutes. The encapsulated photocurable resin composition was cured to produce a cushioning insole that follows the shape of the sole with a maximum thickness of 1.0 cm as the insole.

  The insole obtained in a short time had a good feeling by following the shape of the sole, had a flexibility to absorb the impact, had a good feeling of walking and was not easily fatigued.

(Example 2)
It was obtained in Formulation Example 1 in a bag-like container prepared by bonding a polyurethane elastomer film Higress DU235 (thickness 30 μm) made by Seadam as a soft film and a hard PVC sheet (thickness 200 μm) as another member. The photocurable resin composition [A1] was filled and the filling port was heat-sealed. This package was placed on an acrylic plate with the soft film on top, and in the same manner as in Example 1, a foot was placed on the package to follow the shape of the sole and irradiated with ultraviolet rays for 3 minutes. The encapsulated photocurable resin composition was cured to produce a cushioning insole that follows the shape of the sole with a maximum thickness of 1.0 cm as the insole.

  The insole obtained in a short time has a good feeling by following the shape of the sole, has the flexibility to absorb the impact, has a good walking feeling, and is less tired with little slippage in the shoe. .

Example 3
As a light irradiation device, a maximum thickness of 1.5 cm was obtained in the same manner as in Example 2 except that irradiation was performed for 3 minutes using LED light gel nail digital pro SMLED5 (peak illuminance 9 mW / cm ² (wavelength 405 nm)) manufactured by Japan Nail School. A cushioning insole that follows the shape of the soles was manufactured.

  The insole obtained in a short time had a good feeling by following the shape of the sole, had a flexibility to absorb the impact, had a good feeling of walking and was not easily fatigued.

Example 4
Maximum thickness of 1.4 cm in the same manner as in Example 2 except that irradiation is carried out for 5 minutes using Yanose ROORO CCFL light RO-19 (CCFL) 12 W (peak illuminance 6 mW / cm ² (wavelength 365 nm)). A cushioning insole that follows the shape of the sole was manufactured.

  The insole obtained in a short time had a good feeling by following the shape of the sole, had a flexibility to absorb the impact, had a good feeling of walking and was not easily fatigued.

(Comparative Example 1)
A bag-shaped container prepared by bonding two hard vinyl chloride sheets (thickness: 200 μm) was filled with the photocurable resin composition [A1] obtained in Formulation Example 1, and the filling port was heat-sealed. This package was placed on an acrylic plate, and in the same manner as in Example 1, a foot was placed on it and irradiated with ultraviolet rays for 3 minutes. The encapsulated photocurable resin composition was cured to produce an insole having a maximum thickness of 0.5 cm as an insole. However, it does not follow the shape of the soles, and when worn in shoes, there is a gap between the insole and the soles, which makes it feel uncomfortable, and because of the hardness of the rigid PVC sheet, it makes you feel uncomfortable when walking. I felt.

(Formulation example 2)
As a photocurable resin, 70 parts by weight of the polymer [P2] obtained in Synthesis Example 2 and 30 parts by weight of the polymer [P3] obtained in Synthesis Example 3 were used (average photocrosslinkable group in one molecule). : 1.8), ISTA (isostearyl acrylate, manufactured by Osaka Organic Chemical Co., Ltd.) as a reactive diluent, 100 parts by weight as a plasticizer, 200 parts by weight of DOA (dioctyl adipate, manufactured by Daihachi Chemical), and IRGANOX 1010 (as an antioxidant) A photocurable resin composition [A2] was prepared in the same manner as in Formulation Example 1 except that 0.1 parts by weight of BASF Japan) and 0.2 parts by weight of IRGACURE819 (BASF Japan) were used as a photoinitiator. Obtained. It was E5 when the hardened | cured material was produced by light irradiation and the hardness was measured.

(Formulation example 3)
As a photocurable resin, 50 parts by weight of the polymer [P1] obtained in Synthesis Example 1 and 50 parts by weight of the polymer [P5] obtained in Synthesis Example 5 were used (average photocrosslinkable group in one molecule). : 1.4), 70 parts by weight of DOA (dioctyl adipate manufactured by Daihachi Chemical) as a plasticizer, 0.1 part by weight of IRGANOX1010 (manufactured by BASF Japan) as an antioxidant, DAROCUR1173 (BASF Japan) as a photoinitiator 0.2 parts by weight) and 0.1 part by weight of IRGACURE819 (BASF Japan) were added, sufficiently heated, dissolved and mixed, and then defoamed to obtain a photocurable resin composition [A3]. . The photocurable resin composition [A3] was irradiated with ultraviolet rays at a peak illuminance of 400 mW / cm ² and an integrated light amount of 5000 mJ / cm ² using LH-6 (bulb: H-bulb) manufactured by Heraeus as an ultraviolet irradiation device. A rubber-like molded body having a thickness of 12 mm was produced. When the hardness was measured, it was E9.

(Formulation example 4)
As a photocurable resin, 100 parts by weight of the polymer [P1] obtained in Synthesis Example 1, 0.1 part by weight of IRGANOX1010 (manufactured by BASF Japan) as an antioxidant, and DAROCUR1173 (manufactured by BASF Japan) as a photoinitiator ) Photocurable resin composition [A4] was obtained in the same manner as in Formulation Example 3, except that 0.2 parts by weight and 0.1 part by weight of IRGACURE819 (BASF Japan) were used. When the hardness was measured after light irradiation in the same manner as in Formulation Example 3, it was E40.

(Formulation example 5)
As the photocurable resin, 20 parts by weight of the polymer [P1] obtained in Synthesis Example 1 and 80 parts by weight of the polymer [P4] obtained in Synthesis Example 4 were used (average photocrosslinkable group in one molecule). : 1.1), 10 parts by weight of ACMO (acryloylmorpholine KJ Chemicals) as a reactive diluent and 5 parts of biscoat # 295 (manufactured by Osaka Organic Chemical Co., Ltd.), IRGANOX 1010 (as an antioxidant) Example 3 except that 0.1 part by weight of BASF Japan), 0.2 part by weight of DAROCUR1173 (manufactured by BASF Japan) and 0.1 part by weight of IRGACURE819 (manufactured by BASF Japan) are used as the photoinitiator. Similarly, photocurable resin composition [A5] was obtained. When the hardness was measured after light irradiation in the same manner as in Formulation Example 3, it was E42.

(Formulation example 6)
As a photocurable resin, 70 parts by weight of the polymer [P2] obtained in Synthesis Example 2 and 30 parts by weight of EBECRYL230 (molecular weight: 5000, functional group number: 2 aliphatic urethane acrylate) manufactured by Daicel Ornex Co., Ltd. were used (average) Photo-crosslinkable groups in one molecule: 1.9), ISTA (isostearyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.) 100 parts by weight as a reactive diluent, and DOA (dioctyl adipate, manufactured by Daihachi Chemical) 200 as a plasticizer In the same manner as in Formulation Example 3, except that 0.1 part by weight of IRGANOX 1010 (manufactured by BASF Japan) is used as an antioxidant and 0.2 part by weight of IRGACURE 819 (manufactured by BASF Japan) is used as a photoinitiator, A curable resin composition [A6] was obtained. When the hardness was measured after light irradiation in the same manner as in Formulation Example 3, it was E14.

(Examples 5 to 10)
Instead of the photocurable resin composition [A1], the photocurable resin compositions [A2] to [A6] obtained in Formulation Examples 2 to 6 were used, and the soles were formed in the same manner as in Example 2. The following cushioning insole was manufactured. However, in Examples 5 and 6 using the photocurable resin compositions [A2] and [A3], the irradiation time was 1 minute.

  The insole obtained in a short time had a good feeling by following the shape of the sole, had a flexibility to absorb the impact, had a good feeling of walking and was not easily fatigued.

(Formulation example 7)
As a photocurable resin, 100 parts by weight of the polymer [P2] obtained in Synthesis Example 2 was used (average photocrosslinkable group in one molecule: 1.8), and IRGANOX1010 (manufactured by BASF Japan) as an antioxidant. ) As a photoinitiator and 0.1 part by weight IRGACURE819 (BASF Japan) 0.5 parts by weight was added in the same manner as in Formulation Example 1 to obtain a photocurable resin composition [A7]. . It was E54 when hardened | cured material was produced by light irradiation and the hardness was measured.

Example 11
Using the photocurable resin composition [A7] obtained in Formulation Example 7 in place of the photocurable resin composition [A1], a cushioning insole that follows the sole shape is obtained in the same manner as in Example 2. Manufactured.

  The insole obtained in a short time was not tired during walking because it had a good feeling by following the shape of the sole, and was rich in elasticity and excellent in resilience.

(Formulation example 8)
As photocurable resin, 100 parts by weight of EBECRYL230 (molecular weight 5000, functional number of aliphatic urethane acrylate) manufactured by Daicel Ornex Co., Ltd., 0.1 part by weight of MARK AO-50 (manufactured by ADEKA) as an antioxidant As a photoinitiator, 0.2 parts by weight of DAROCUR 1173 (manufactured by BASF Japan) and 0.1 part by weight of IRGACURE819 (manufactured by BASF Japan) are added, dissolved and mixed, defoamed, and photocured. A resin composition [A8] was obtained. The photocurable resin composition [A8] was irradiated with ultraviolet rays at a peak illuminance of 500 mW / cm ² and an integrated light amount of 2000 mJ / cm ² using Heraeus LH-6 (bulb: H-bulb) as an ultraviolet irradiation device. A rubber-like molded body having a thickness of 2 mm was produced. The hardness was measured and found to be E65.

(Example 12)
Instead of the photocurable resin composition [A1], the photocurable resin composition [A8] obtained in Formulation Example 8 is used, and a cotton fabric is bonded on the soft urethane film (the side in contact with the sole). A cushioning insole that follows the shape of the sole was manufactured in the same manner as in Example 2 except that.

  The insole obtained in a short time was excellent in fixability in addition to a good feeling by following the sole shape, and was effective in posture correction during standing and walking.

(Formulation example 9)
As a photocurable resin, 90 parts by weight of EBECRYL230 (molecular weight 5000, functional group number: 2 aliphatic urethane acrylate) manufactured by Daicel Ornex Co., Ltd. and EBECRYL5129 (molecular weight 800, functional group number: 6 aliphatic groups manufactured by Daicel Ornex Co., Ltd.) are used. Acrylate) 10 parts by weight (average photocrosslinkable group in one molecule: 2.4), DAROCUR1173 (manufactured by BASF Japan) as photoinitiator 0.2 part by weight and IRGACURE819 (manufactured by BASF Japan) ) 0.1 part by weight was added, and after sufficient dissolution and mixing, defoaming was performed to obtain a photocurable resin composition [A9]. The photocurable resin composition [A9] was irradiated with ultraviolet rays at a peak illuminance of 500 mW / cm ² and an integrated light amount of 2000 mJ / cm ² using Heraeus LH-6 (bulb: H-bulb) as an ultraviolet irradiation device. A rubber-like molded body having a thickness of 2 mm was produced. The hardness was measured and found to be E74.

(Example 13)
Cushioning property that follows the sole shape in the same manner as in Example 12 except that the photocurable resin composition [A9] obtained in Formulation Example 9 is used instead of the photocurable resin composition [A1]. An insole was manufactured.

  The insole obtained in a short time was excellent in fixability in addition to a good feeling by following the sole shape, and was effective in posture correction during standing and walking.

(Comparative Formulation Example 1)
As a photo-curable resin, 15 parts by weight of EBECRYL230 (molecular weight 5000, functional group number: 2 aliphatic urethane acrylate) manufactured by Daicel Ornex Co., Ltd. and EBECRYL 5129 (molecular weight 800, functional group number: 6 aliphatic groups manufactured by Daicel Ornex Co., Ltd.) are used. (Acrylate) 85 parts by weight (average photocrosslinkable group in one molecule: 2.6), DAROCUR1173 (manufactured by BASF Japan) as photoinitiator 0.2 part by weight and IRGACURE819 (manufactured by BASF Japan) ) 0.1 part by weight was added, and after sufficiently dissolving and mixing, defoaming was performed to obtain a photocurable resin composition [A10]. The photocurable resin composition [A10] was irradiated with ultraviolet rays at a peak illuminance of 500 mW / cm ² and an integrated light amount of 2000 mJ / cm ² using Heraeus LH-6 (bulb: H-bulb) as an ultraviolet irradiation device. A rubber-like molded body having a thickness of 2 mm was produced. The hardness was measured and found to be E81.

(Comparative Example 2)
Example 2 except that instead of the photocurable resin composition [A1], the photocurable resin composition [A10] obtained in Comparative Formulation Example 1 was used, and a flexible urethane film having a thickness of 50 μm was used. Similarly, a cushioning insole following the sole shape was manufactured.

  The insole obtained in a short time follows the sole shape, but has a poor feel due to poor flexibility and elasticity, and is somewhat painful when walking in a shoe.

(Comparative Formulation Example 2)
As a photocurable resin, 100 parts by weight of EBECRYL5129 (molecular weight 800, functional group number: 6 aliphatic urethane acrylate) manufactured by Daicel Ornex Co., Ltd., 0.2 parts by weight of DAROCUR1173 (manufactured by BASF Japan) as a photoinitiator And 0.1 part by weight of IRGACURE819 (manufactured by BASF Japan) was sufficiently dissolved and mixed, and then defoamed to obtain a photocurable resin composition [A11]. The photocurable resin composition [A11] was irradiated with ultraviolet rays at a peak illuminance of 500 mW / cm ² and an integrated light amount of 2000 mJ / cm ² using Heraeus LH-6 (bulb: H-bulb) as an ultraviolet irradiation device. A resinous molded body having a thickness of 2 mm was prepared. When the hardness was measured, it was out of the measurement range (100 or more) with a Type E durometer.

(Comparative Example 3)
Example 2 except that the photocurable resin composition [A11] obtained in Comparative Formulation Example 2 was used instead of the photocurable resin composition [A1], and a flexible urethane film having a thickness of 50 μm was used. Similarly, an attempt was made to produce a cushioning insole that follows the shape of the sole.

  However, since the temperature became high due to the heat of curing during the irradiation and there was a possibility of causing burns, the irradiation was stopped in the middle and an insole could not be obtained.

  As described above, in order to obtain an insole that follows the shape of the sole, it is necessary to use a soft film as a material of the package. Further, regarding the enclosed photocurable resin composition, It is necessary to select the structure appropriately.

Claims (14)

The photocurable resin composition (B) is encapsulated in a member containing the soft film (A) in advance, and the photocurable resin composition (B) is irradiated by irradiating light with the soft film pressed against the sole. A method of manufacturing an insole shaped into a sole shape by curing,
The photocurable resin composition (B) includes a photocurable resin (I) having an average of 0.9 to 2.5 photocrosslinkable groups in one molecule and a photoinitiator (II). A method for producing an insole characterized by the above. The method for producing an insole according to claim 1, wherein the member is a composite member of a flexible film (A) and another member (C). The method for producing an insole according to claim 1 or 2, wherein the hardness of the photocurable resin composition (B) after curing is E80 or less with a type E hardness meter. The soft film (A) is one using any one soft material selected from polyvinyl chloride, polyolefin, polyurethane, and ethylene / vinyl acetate copolymer. A method for producing the insole according to claim 1. The photocurable resin (I) is at least one photocured selected from urethane (meth) acrylate, epoxy (meth) acrylate, ester (meth) acrylate, silicone (meth) acrylate, and acrylic (meth) acrylate The method for producing an insole according to any one of claims 1 to 4, wherein the insole is a functional resin. The photocrosslinkable group possessed by the photocurable resin (I) has the general formula (1):
—OC (O) C (R ¹ ) ═CH ₂ (1)
(Wherein, R ¹ represents a hydrogen atom or an organic group having 1 to 20 carbon atoms) production of insole according to any one of claims 1 to 5, characterized in that a (meth) acryloyl group represented by Method. The method for producing an insole according to any one of claims 1 to 6, wherein the photocurable resin (I) has at least 0.8 photocrosslinkable groups at the molecular chain terminals. The method for producing an insole according to any one of claims 1 to 7, wherein the photocurable resin (I) has a molecular weight of 1,000 or more. The method for producing an insole according to any one of claims 1 to 8, wherein the photocurable resin (I) is a (meth) acrylic polymer synthesized by a living radical polymerization method. The method for producing an insole according to any one of claims 1 to 9, wherein the photoinitiator (II) is 0.01 to 10 parts by weight with respect to 100 parts by weight of the photocurable resin (I). The method for producing an insole according to any one of claims 1 to 10, wherein the irradiated light is light having a peak illuminance at a wavelength of 350 nm or more. The insole manufacturing method according to any one of claims 1 to 11, wherein the light source to be irradiated is LED light having a peak illuminance at a wavelength of 400 nm or more. The method for producing an insole according to any one of claims 1 to 12, wherein a peak illuminance of the irradiated light is 20 mW / cm ² or less. An insole obtained by the production method according to claim 1.