JP2005342927A - Resin mold and manufacturing method of cured resin molded product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin mold constituted so as to obtain a cured resin molded product having high surface precision, making the adhesiveness with the cured resin molded product proper and excellent in the productivity of the resin mold itself. <P>SOLUTION: The resin mold for molding a curable resin is manufactured by molding a resin composition, which is prepared by adding 0.01-20 pts.wt. of a fatty acid monoester of a trivalent or above polyhydric alcohol to 100 pts.wt. of an alicyclic structure-containing polymer with a melt flow rate of 1-150 g/10 min, and characterized in that the surface coming into contact with the curable resin thereof has a surface roughness of 0.001-1.5 μm and the contact angle θ with water thereof is 10-95°. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a resin mold, and more specifically, there is little mold contamination during molding of the resin mold itself, the adhesion between a cured resin molded body molded using the resin mold and the resin mold is moderate, and the surface The present invention relates to a resin mold from which a cured resin molded body with few defects is obtained.

Resin made of polycarbonate or polymethacrylate as a simple method for producing sheet-like or plate-like plastic moldings with irregularities on the surface, such as compact discs, lenticular lenses, Fresnel lenses, prism sheets, and light guide plates A method in which a mold is filled with a polymerizable monomer such as acrylate and then cured by irradiating with ultraviolet rays.
However, in these methods, since the resin mold is deformed due to humidity, polymerization heat during polymerization, etc., there is a problem that the fine uneven shape of the molded body is distorted, the resin mold and the cured molded body Since the releasability is poor, there is a problem that the molded body is easily damaged particularly in a thin and large molded body and a problem that the uneven shape cannot be transferred sufficiently.
In order to solve these problems, Patent Document 1 discloses that an alicyclic structure-containing thermoplastic resin (corresponding to the alicyclic structure-containing polymer of the present application) is used as a resin-type resin material, and that the resin mold and curability are used. It is disclosed that a release agent is added for the purpose of further improving the releasability with the resin.

JP 2000-108137 A

Recent cured resin moldings are required to have higher accuracy than conventional ones. Therefore, in order to prevent the curable resin adhering to the resin mold when the resin mold is repeatedly used from adversely affecting the surface accuracy of the cured resin molded body, the resin mold is becoming disposable.
Therefore, it is necessary to mass-produce resin molds, and the productivity of the resin mold itself is also required.
On the other hand, in the manufacturing process of the cured resin molded body using the resin mold, there is a process of peeling the concave resin mold and the convex resin mold from the cured resin molded body, but in order to automate the peeling process, one resin mold is used. The mold separation selectivity of peeling the other resin mold from the cured resin molded body with the cured resin molded body attached is essential.
However, the resin mold described in Patent Document 1 has insufficient releasability from the mold used for molding the resin mold, or the mold is contaminated with a mold release agent and needs to be frequently cleaned. The present inventors have found that there is a problem that the productivity of the mold itself is inferior and a problem that the mold release selectivity is low because the adhesion between the resin mold and the cured resin molding is too low.
Accordingly, an object of the present invention is a resin mold having a high surface accuracy of the obtained cured resin molded article, which has an appropriate adhesion between the resin mold and the cured resin molded article, and is excellent in the productivity of the resin mold itself. To provide a mold.

  As a result of diligent investigations to solve the above problems, the present inventors have released a specific amount of a fatty acid monoester of a trihydric or higher polyhydric alcohol into an alicyclic structure-containing polymer having a specific range of melt flow rate. When the surface roughness of the resin mold is kept in a certain range and the contact angle θ with water is kept in a certain range, the surface accuracy of the resulting cured resin molded article is high, and the resin mold and the cured resin molded article are used. The present inventors have found that the adhesiveness of the resin is moderate and the productivity of the resin mold itself is excellent, and the present invention has been completed.

Thus, according to the present invention,
A resin mold for molding a curable resin,
Melt flow rate is 1-150 g / 10 min. A resin composition (a) containing 0.01 to 20 parts by weight of a trihydric or higher polyhydric alcohol fatty acid monoester with respect to 100 parts by weight of the alicyclic structure-containing polymer in the range of
Of the surface in contact with the curable resin,
The surface roughness is in the range of 0.001 to 1.5 μm,
A resin mold having a contact angle θ with water in the range of 10 to 95 degrees is provided.
The fatty acid monoester of the polyhydric alcohol is preferably glycerin monostearate, more preferably the tensile elongation of the resin composition (a) is 40% or more, and the resin mold thickness is in the range of 0.5 to 2 mm. Is particularly preferred.
Furthermore, the above-mentioned resin mold (resin mold (A)) and melt flow rate are 1-150 g / 10 min. A resin composition comprising an alicyclic structure-containing polymer in the range of the above, wherein the content ratio of a fatty acid monoester of a trihydric or higher polyhydric alcohol relative to the alicyclic structure-containing polymer is (1) Resin mold (B) formed by molding less resin composition (b) than a)
A composite resin mold is provided.
According to this invention, the cured resin molded object shape | molded using the said resin type | mold is provided.
Also, a step of curing and molding the curable resin in the space formed by the resin mold (A) and the resin mold (B) described above, and the obtained cured resin molded body was adhered to the resin mold (A). A method for producing a cured resin molded article comprising a step of peeling the cured resin molded article from the resin mold (A) after peeling from the resin mold (B) in a state, and a cured resin molded article obtained by the production method are provided. Is done.

  The resin mold of the present invention has excellent mold releasability between the mold and the resin mold when molding the resin mold itself, and is excellent in productivity of the resin mold itself because the mold is less contaminated. When molding a curable resin using a mold, the adhesive strength between the resin mold and the resulting cured resin molded article is moderate, so other resins can be used with the cured resin molded article attached to a specific resin mold. Since the mold can be peeled off, the productivity of the cured resin molded product is excellent, and the resulting cured resin molded product has few surface defects.

  The resin mold of the present invention is formed by molding a resin composition (a) containing an alicyclic structure-containing polymer and a fatty acid monoester of a trihydric or higher polyhydric alcohol.

(Aricyclic structure-containing polymer)
The alicyclic structure-containing polymer used in the present invention is a polymer containing an alicyclic structure in the repeating unit of the polymer, and has an alicyclic structure in either the main chain or the side chain. Also good.
Examples of the alicyclic structure include a cycloalkane structure and a cycloalkene structure, and a cycloalkane structure is preferable from the viewpoint of the thermal stability of the polymer.
The number of carbon atoms constituting the alicyclic structure is usually in the range of 4 to 30, preferably 5 to 20, and more preferably 5 to 15. When the number of carbon atoms is within this range, it is preferable from the viewpoint of the heat resistance of the obtained resin mold.
The proportion of the repeating unit having an alicyclic structure in the alicyclic structure-containing polymer may be appropriately selected according to the purpose of use, but is usually 50% by weight or more, preferably 70% by weight or more, more preferably 90% by weight or more. When the ratio of the repeating unit having an alicyclic structure in the alicyclic structure-containing polymer is within this range, it is preferable from the viewpoint of the heat resistance of the obtained resin mold.
In addition, the remainder other than the repeating unit which has an alicyclic structure in an alicyclic structure containing polymer is suitably selected according to the intended purpose.

Specific examples of the alicyclic structure-containing polymer include (1) norbornene polymer, (2) monocyclic olefin polymer, (3) cyclic conjugated diene polymer, and (4) vinyl alicyclic hydrocarbon. Examples thereof include polymers and hydrides thereof.
Among these, norbornene polymers, cyclic conjugated diene polymers, vinyl alicyclic hydrocarbon polymers, and hydrides thereof are preferable from the viewpoint of heat resistance, mechanical strength, and the like of the obtained resin mold. Polymers, vinyl alicyclic hydrocarbon polymers and their hydrides are more preferred, and hydrides of norbornene polymers are particularly preferred.

(1) Norbornene-based polymer The norbornene-based polymer includes a ring-opening polymer of a norbornene-based monomer, a ring-opening copolymer of a norbornene-based monomer and other monomers capable of ring-opening copolymerization, and hydrides thereof. Addition polymers of norbornene monomers, addition copolymers of norbornene monomers and other monomers copolymerizable therewith, and the like. Among these, a ring-opening polymer hydride of a norbornene monomer is most preferable from the viewpoints of the heat resistance and mechanical strength of the obtained resin mold.

ノルボルネン系モノマーとしては、ビシクロ［２．２．１］ヘプト−２−エン（慣用名：ノルボルネン）及びその誘導体（環に置換基を有するもの）、トリシクロ［４．３．０．１^２，５］デカ−３，７−ジエン（慣用名：ジシクロペンタジエン）及びその誘導体、テトラシクロ［７．４．０．０^２，７．１^{１０，１３}］トリデカ−２，４，６，１１−テトラエン（慣用名：メタノテトラヒドロフルオレン）及びその誘導体、テトラシクロ［４．４．０．１^２，５．１^７，１０］ドデカ−３−エン（慣用名：テトラシクロドデセン）及びその誘導体などが挙げられる。
置換基としては、アルキル基、アルキレン基、ビニル基、アルコキシカルボニル基などが例示でき、上記ノルボルネン系モノマーは、これらを２種以上有していてもよい。
具体的には、８−メトキシカルボニル−テトラシクロ［４．４．０．１^２，５．１^７，１０］ドデカ−３−エン、８−メチル−８−メトキシカルボニル−テトラシクロ［４．４．０．１^２，５．１^７，１０］ドデカ−３−エンなどが挙げられる。これらのノルボルネン系モノマーは、それぞれ単独であるいは２種以上を組み合わせて用いられる。 In the present invention, the norbornene-based monomer is a compound having a norbornene structure represented by the formula (1).

As norbornene-based monomers, bicyclo [2.2.1] hept-2-ene (common name: norbornene) and its derivatives (having a substituent in the ring), tricyclo [4.3.0.1 ^2,5 ] Deca-3,7-diene (common name: dicyclopentadiene) and derivatives thereof, tetracyclo [7.4.0.0 ^2,7 . 1 ^10,13] trideca -2,4,6,11- tetraene (common name: methanolate tetrahydrofluorene) and derivatives thereof, tetracyclo [4.4.0.1 ^{2, 5. 17, 10} ] dodec-3-ene (common name: tetracyclododecene) and its derivatives.
Examples of the substituent include an alkyl group, an alkylene group, a vinyl group, and an alkoxycarbonyl group, and the norbornene-based monomer may have two or more of these.
Specifically, 8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene and the like. These norbornene monomers are used alone or in combination of two or more.

Ring-opening polymers of these norbornene monomers, or ring-opening copolymers of norbornene monomers and other monomers capable of ring-opening copolymerization are polymerized in the presence of a known ring-opening polymerization catalyst. Can be obtained.
Ring-opening polymerization catalysts include metal halides such as ruthenium and osmium, nitrates or acetylacetone compounds, and reducing agents; metal halides or acetylacetone compounds such as titanium, zirconium, tungsten and molybdenum, and organoaluminum. And a catalyst comprising a cocatalyst such as a compound.

  Examples of other monomers capable of ring-opening copolymerization with norbornene monomers include monocyclic olefin monomers such as cyclohexene, cycloheptene, and cyclooctene.

  The ring-opening polymer hydride of a norbornene-based monomer is usually prepared by adding a known hydrogenation catalyst containing a transition metal such as nickel or palladium to the polymerization solution of the above-mentioned ring-opening polymer so that the carbon-carbon unsaturated bond is hydrogenated. Can be obtained.

  Addition polymers of norbornene monomers, or addition copolymers of norbornene monomers and other monomers copolymerizable therewith, these monomers can be combined with known addition polymerization catalysts such as titanium, zirconium or vanadium compounds. It can be obtained by (co) polymerization using a catalyst comprising an organoaluminum compound.

  Other monomers that can be copolymerized with norbornene monomers include, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1 A C2-C20 α-olefin such as hexadecene, 1-octadecene, 1-eicocene, and derivatives thereof; cyclobutene, cyclopentene, cyclohexene, cyclooctene, 3a, 5,6,7a-tetrahydro-4,7- Cycloolefins such as methano-1H-indene, and derivatives thereof; non-conjugated such as 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene Diene; etc. are used. Among these, an α-olefin, particularly ethylene is preferable.

  These other monomers capable of addition copolymerization with the norbornene-based monomer can be used alone or in combination of two or more. In the case of addition copolymerization of a norbornene monomer and another monomer capable of addition copolymerization, a structural unit derived from a norbornene monomer in the addition copolymer and a structural unit derived from another monomer capable of copolymerization are used. The ratio is appropriately selected so that it is usually in the range of 30:70 to 99: 1, preferably 50:50 to 97: 3, more preferably 70:30 to 95: 5 by weight.

(2) Monocyclic Cyclic Olefin Polymer Examples of the monocyclic cycloolefin polymer include addition polymers of monocyclic cycloolefin monomers such as cyclohexene, cycloheptene, and cyclooctene.

(3) Cyclic conjugated diene polymer Examples of the cyclic conjugated diene polymer include polymers obtained by subjecting a cyclic conjugated diene monomer such as cyclopentadiene and cyclohexadiene to 1,2- or 1,4-addition polymerization, and hydrides thereof. .

  The molecular weight of the norbornene-based polymer, monocyclic olefin polymer or cyclic conjugated diene polymer is appropriately selected according to the purpose of use, but is a gel of cyclohexane solution (or toluene solution if the polymer resin does not dissolve). Polyisoprene or polystyrene-equivalent weight average molecular weight measured by permeation chromatography, and is usually from 5,000 to 500,000, preferably from 8,000 to 200,000, more preferably from 10,000 to 100,000. When it is within the range, the moldability of the obtained resin composition and the mechanical strength of the obtained resin mold are highly balanced, which is preferable.

(4) Vinyl alicyclic hydrocarbon polymer As the vinyl alicyclic hydrocarbon polymer, polymers of vinyl alicyclic hydrocarbon monomers such as vinylcyclohexene and vinylcyclohexane and their hydrides; styrene, α-methyl Hydrides of aromatic ring moieties of polymers of vinyl aromatic monomers such as styrene; and the like, and vinyl alicyclic hydrocarbon polymers and vinyl aromatic monomers and other copolymerizable with these monomers Any of random copolymers with monomers, copolymers such as block copolymers, and hydrides thereof may be used. Examples of the block copolymer include diblock, triblock, or more multiblock and gradient block copolymers, and are not particularly limited.

  The molecular weight of the vinyl alicyclic hydrocarbon polymer is appropriately selected according to the purpose of use, but it is determined by a gel permeation chromatographic method using a cyclohexane solution (a toluene solution when the polymer resin does not dissolve). The weight average molecular weight in terms of isoprene or polystyrene is usually in the range of 10,000 to 300,000, preferably 15,000 to 250,000, more preferably 20,000 to 200,000. When the weight average molecular weight is within this range, the molding processability of the obtained resin composition and the mechanical strength of the obtained resin mold are highly balanced, which is preferable.

The melt flow rate (MFR) of the alicyclic structure-containing polymer used in the present invention is 1 to 100 g / 10 min. It is in the range.
Especially, MFR is 2-70 g / 10min. Is preferably in the range of 3 to 50 g / 10 min. It is more preferable to be in the range. It is preferable at the point of the moldability of the resin composition obtained that MFR exists in this range.
In the present invention, the melt flow rate (MFR) is a value measured according to JIS-K7210 under conditions of a temperature of 280 ° C. and a load of 2.16 kg.

  The glass transition temperature (Tg) of the alicyclic structure-containing polymer used in the present invention may be appropriately selected according to the purpose of use, but is preferably 70 ° C or higher, and is in the range of 100 to 250 ° C. More preferably, it is in the range of 100 to 200 ° C, particularly preferably in the range of 100 to 140 ° C. When the Tg is within this range, the moldability of the resulting resin composition and the heat resistance of the resulting resin mold are highly balanced, which is preferable.

Various additives can be blended in the alicyclic structure-containing polymer used in the present invention, if necessary.
Compounding agents include antioxidants, heat stabilizers, light stabilizers, weathering stabilizers, etc .; resin modifiers such as plasticizers; antistatic agents; other types of polymers (rubbers and resins) And so on. These compounding agents can be used alone or in combination of two or more thereof, and the compounding amount is appropriately selected within a range not impairing the object of the present invention.
Examples of the antioxidant include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, etc. Among them, phenolic antioxidants, particularly alkyl-substituted phenolic antioxidants are preferable. By blending these antioxidants, it is possible to prevent the resin mold from being colored and the strength from being lowered due to oxidative degradation during the molding of the resin mold without lowering the UV transmittance of the resin mold. These antioxidants may be used alone or in combination of two or more. The amount of the antioxidant is appropriately selected within a range not impairing the object of the present invention, but is usually 0.001 to 5 parts by weight, preferably 0.01 to 100 parts by weight of the alicyclic structure-containing polymer. -1 part by weight.

  Other types of polymers (rubber and resin) include olefin polymers such as polyethylene and polypropylene; isobutylene polymers such as polyisobutylene and isobutylene / isoprene rubber; polybutadiene, polyisoprene, and butadiene / styrene random copolymers , Isoprene / styrene random copolymer, acrylonitrile / butadiene copolymer, acrylonitrile / butadiene / styrene copolymer, butadiene / styrene / block copolymer, styrene / butadiene / styrene / block copolymer, isoprene / styrene / block Copolymer, diene polymer such as styrene / isoprene / styrene block copolymer; acrylic polymer such as polybutyl acrylate and polyhydroxyethyl methacrylate; polyvinyl alcohol, Polymers of vinyl compounds, such as vinyl acetate, vinyl acetate / styrene copolymer; Epoxy polymers, such as polyethylene oxide, polypropylene oxide, epichlorohydrin rubber; Fluorine, such as vinylidene fluoride rubber, tetrafluoroethylene-propylene rubber And the like. These polymers may have a crosslinked structure, or may have a functional group introduced by a modification reaction. Among the above polymers, a diene polymer is preferable in terms of rubber elasticity, mechanical strength, flexibility, and dispersibility, and a hydride obtained by hydrogenating a carbon-carbon unsaturated bond of the polymer is particularly preferable.

(Fatty acid monoester of trihydric or higher polyhydric alcohol)
The fatty acid monoester of a trihydric or higher polyhydric alcohol used in the present invention is a compound in which one of the hydroxyl groups of a trihydric or higher polyhydric alcohol is esterified with a fatty acid.
Examples of fatty acid monoesters of trihydric or higher polyhydric alcohols include glycerol monostearate, glycerol monolaurate, glycerol monomyristate, glycerol monopalmitate, glycerol monobehenate, glycerol monocaprate, glycerol monooleate, and the like. Among them, glycerin is highly balanced between the mold release properties of the resin mold and the mold for molding the resin mold itself, low mold contamination, and mold release selectivity between the resin mold and the cured resin molded body. Monostearate is preferred.

  In the resin composition (a) used in the present invention, the content ratio of the fatty acid monoester of a trihydric or higher polyhydric alcohol with respect to 100 parts by weight of the alicyclic structure-containing polymer is in the range of 0.01 to 20 parts by weight. is there. Among them, it is preferably in the range of 0.1 to 15 parts by weight, more preferably in the range of 1 to 10 parts by weight, and more preferably in the range of 2 to 5 parts by weight.

(Resin composition (a))
As a method for producing the resin composition (a) used in the present invention, the alicyclic structure-containing polymer, a trihydric or higher polyhydric alcohol fatty acid monoester, and a compounding agent blended as necessary. A method of obtaining a pellet-shaped resin composition by kneading; an alicyclic structure-containing polymer in a suitable solvent, a fatty acid monoester of a trihydric or higher polyhydric alcohol, and a compounding agent blended as necessary And a method of obtaining a resin composition by removing the solvent.

  For kneading, a melt kneader such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a kneader, or a feeder ruder can be used. The kneading temperature is preferably in the range of 180 to 400 ° C, and more preferably in the range of 200 to 350 ° C. Further, when kneading, the components may be added together and kneaded, or may be kneaded while adding in several times.

The tensile elongation of the resin composition (a) used in the present invention is not particularly limited, but is preferably in the range of 30% to 200%, more preferably in the range of 40% to 180%, and 100% to 150%. It is especially preferable that it is in the range.
When the tensile elongation of the resin composition (a) is within this range, the resin mold can be deformed when the resin mold is peeled from the cured resin molded article, so that the ease of peeling and the prevention of breakage of the resin mold are possible. Is preferable.
In the present invention, the tensile elongation (%) is 5 mm / min. It is the value measured according to ASTM-D-638 under the conditions.

(Resin mold molding method)
The resin composition (a) can be formed into a resin mold using a known molding means such as an injection molding method, a compression molding method, an extrusion molding method and the like. The shape of the resin mold can be appropriately selected according to the application.

The molding conditions are not particularly limited, but the resin temperature during molding is usually 200 ° C to 400 ° C, preferably 210 ° C to 350 ° C. In addition, when using a mold, the mold temperature t ₀ ° C is usually room temperature <t ₀ <(t ₁ +15) ° C, where the glass transition temperature of the alicyclic structure-containing polymer used is t ₁ ° C. Preferably, (t ₁ -30) <t ₀ <(t ₁ +10) ° C., more preferably (t ₁ -20) <t ₀ <(t ₁ +5) ° C. (however, (t ₁ -30) <If room temperature or (t ₁ -20) ° C. <room temperature, room temperature <t ₀ ° C.). When the resin temperature and mold temperature at the time of molding are in this range, it is preferable from the viewpoint of mold releasability between the mold and the resin mold.

(Resin mold)
The resin mold of the present invention is used for molding a curable resin.
The surface roughness of the surface in contact with the curable resin of the resin mold of the present invention is in the range of 0.001 to 1.5 μm and the contact angle θ with water is in the range of 10 to 95 degrees.

The surface roughness of the surface in contact with the curable resin is preferably in the range of 0.05 to 1 μm, and more preferably in the range of 0.05 to 0.5 μm.
In the present invention, the surface roughness is a value measured in accordance with JIS-B0601 using a surface roughness meter (manufactured by Rank Taylor Hobson; Form Talysurf).
The surface roughness of the surface in contact with the curable resin can be adjusted by lapping polishing the surface of the mold used for molding the resin mold.

The contact angle θ with water on the surface in contact with the curable resin is preferably in the range of 10 to 80 degrees, and more preferably in the range of 10 to 60 degrees.
In the present invention, the contact angle with water is a value measured by the θ / 2 method using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd .; DropMaster 300) in an environment of temperature 25 ° C./humidity 50%.
The contact angle θ with water on the surface in contact with the curable resin can be adjusted by the type and blending amount of the fatty acid monoester of a trihydric or higher polyhydric alcohol.

The thickness of the resin mold of the present invention is not particularly limited, but is preferably in the range of 0.5 to 2 mm, more preferably in the range of 0.5 to 1.5 mm, and in the range of 0.6 to 1.0 mm. It is particularly preferred that
When the thickness of the resin mold is within this range, the resin mold has an appropriate flexibility so that when the resin mold is peeled from the cured resin molded body, the resin mold can be peeled while being deformed. Peeling from the resin molded body is easy and it is difficult to damage the surface of the cured resin molded body.

  The resin mold of the present invention can be used for molding a cured resin molded body that cures a curable resin filled in a space formed by the resin mold.

(Curable resin)
The curable resin is not particularly limited, and those generally used in the resin industry can be used, and those containing a polymerizable monomer and a polymerization initiator are usually used.

As the polymerizable monomer, a radical polymerizable monomer is usually used.
Examples of the radical polymerizable monomer include compounds containing one or more vinyl groups, (meth) allyl groups, acrylic groups or methacryl groups in the molecule. Among these, compounds containing one or more methacryl groups in the molecule. However, since it is excellent in properties such as heat resistance, transparency, and immediate curing property of the curable resin, it is suitable for optical parts.

  Specifically, alkyl (meth) acrylate, siloxanyl (meth) acrylate, fluoroalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, polyethylene glycol (meth) acrylate, (meth) acrylic acid ester of polyhydric alcohol, vinyl (Meth) acrylates such as (meth) acrylates, styrene derivatives, N-vinyl lactam, vinyl compounds such as (polyvalent) vinyl carboxylates, and the like.

More specifically, styrene, acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, phenyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate. , 2-ethylhexyl methacrylate, isobornyl methacrylate, benzyl methacrylate, phenyl methacrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, tri Methylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, 1,4 Butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, divinylbenzene diallyl phthalate, diethylene glycol bisallyl carbonate, 2-methacryloyloxyethyl succinic acid, 2-hydroxyethyl methacrylate , 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, fumaric acid and esters thereof, methacrylonitrile, N, N-dimethylacrylamide, N-vinyl-2-pyrrolidone, 2-methacryloyloxyethyl phosphorylcholine and the like. .
These polymerizable monomers can be used alone or in combination of two or more.

The polymerization initiator may be either a thermal polymerization initiator or a photopolymerization initiator, but a photopolymerization initiator is preferable from the viewpoint of productivity.
As photopolymerization initiators, benzoin, benzoin monomethyl ether, benzoin isopropyl ether, acetoin, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, benzyldimethyl ketal, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, methyl Carbonyl compounds such as phenylglyoxylate, ethylphenylglyoxylate, 2-humanoxy-2-methyl-1-phenylpropan-1-one, 2-ethylanthraquinone; sulfur compounds such as tetramethylthiuram monosulfide; 2,6 -Acylphosphine oxides such as dimethylbenzoyldiphenylphosphine oxide and 2,4,6-trimethylbenzoylphenylphosphine oxide; .
Examples of the thermal polymerization initiator include benzoyl peroxide, diisopropyl peroxycarbonate, t-butyl peroxy (2-ethylhexanoate) and the like.
These polymerization initiators can be used alone or in combination of two or more.

  Although the compounding quantity of a polymerization initiator is suitably selected according to a use purpose, it is 0.001-5 weight part normally per 100 weight part of polymerizable monomers, Preferably it is the range of 0.01-1 weight part. When the compounding agent for the polymerization initiator is within this range, even a large molded product can be uniformly cured, and there is no spots or yellowing, and a colored product can be produced with good productivity.

  The method of using the resin mold of the present invention is not particularly limited, but a method of curing after filling a space formed by combining resin molds having different shapes or physical properties, after applying the curable resin to the resin mold. Further, there are a method of curing the curable resin after laminating the resin mold, a method of curing the curable resin after further laminating the resin mold after applying the curable resin on the molded body, and the like.

Moreover, the hardening method of curable resin is not specifically limited.
Specifically, a method of using a curable resin containing a polymerizable monomer and a photopolymerization initiator as a curable resin, filling the resin mold, and irradiating with active energy rays to cure; a polymerizable monomer as the curable resin; And a method in which a thermosetting resin containing a thermal polymerization initiator is used and the resin mold is filled and then heated and cured.

  The resin mold of the present invention (denoted as resin mold (A)) is preferably used as a composite resin mold comprising a resin mold (A) and a resin mold (B).

The resin mold (B) used in the present invention has a melt flow rate of 1 to 150 g / 10 min. The resin composition (b) containing the alicyclic structure-containing polymer in the range of is formed.
In the present invention, the melt flow rate (MFR) is a value measured according to JIS-K7210 under conditions of a temperature of 280 ° C. and a load of 2.16 kg.

Examples of the alicyclic structure-containing polymer contained in the resin composition (b) include alicyclic structure-containing polymers that can be used in the resin composition (a).
The resin composition (b) may contain a fatty acid monoester of a trihydric or higher polyhydric alcohol, a compounding agent that can be used for the resin composition (a), and the like.

  Although the content ratio of the fatty acid monoester of a trihydric or higher polyhydric alcohol to the alicyclic structure-containing polymer in the resin composition (b) is not particularly limited, a resin used for molding the resin mold (A) to be used together It is preferable that it is a ratio smaller than the content rate of the fatty acid monoester of the trihydric or more polyhydric alcohol with respect to the alicyclic structure containing polymer in a composition (a). Among them, the resin composition used in the molding of the resin mold (A) in which the content ratio of the trivalent or higher fatty acid monoester to the alicyclic structure-containing polymer in the resin composition (b) is used in combination. It is more preferable that it is 9/10 or less of the content ratio of the fatty acid monoester of a polyhydric alcohol having a valence of 3 or more with respect to the alicyclic structure-containing polymer in (a), particularly preferably 1/2 or less, and 1/10. Most preferred is

  When the resin mold (A) is used as a composite resin mold in combination with the resin mold (B), the resin mold (A) / cured resin molded body / resin obtained after a step of curing and molding the curable resin When the resin mold (A) and the resin mold (B) are peeled from the composite of the mold (B), the cured resin is peeled off from the resin mold (B) while being attached to the resin mold (A). Since the molded body can be peeled from the resin mold (A), the peeling process of the resin mold can be automated, which is preferable in terms of productivity of the cured resin molded body.

The surface roughness of the surface in contact with the curable resin of the resin mold (B) is not particularly limited, but the surface roughness is preferably in the range of 0.05 to 1 μm, and in the range of 0.05 to 0.5 μm. More preferred.
The contact angle θ ′ with the water on the surface in contact with the curable resin of the resin mold (B) is not particularly limited, but the relationship with the contact angle θ with the water on the surface in contact with the curable resin of the resin mold (A) is A relationship of θ + 10 <θ ′ is preferable, a relationship of θ + 30 <θ ′ is more preferable, and a relationship of θ + 60 <θ ′ is particularly preferable.

The thickness of the resin mold (B) is not particularly limited, but is preferably in the range of 0.5 to 2 mm, more preferably in the range of 0.5 to 1.5 mm, and in the range of 0.6 to 1.0 mm. It is particularly preferred that
When the thickness of the resin mold (B) is within this range, the resin mold has an appropriate flexibility so that the resin mold can be peeled while being deformed when the resin mold is peeled from the cured resin molded body. Therefore, it is preferable because peeling from the cured resin molded body is easy and the surface of the cured resin molded body is difficult to be damaged.

The resin mold of the present invention has excellent mold releasability between the mold and the resin mold when molding the resin mold itself, and is excellent in productivity of the resin mold itself because there is little dirt on the mold.
In addition, the resin mold of the present invention has an appropriate adhesive force between the resin mold and the obtained cured resin molded article when molding the curable resin, so that the cured resin molded article is attached to a specific resin mold. Since the other resin molds can be peeled as they are, the productivity of the cured resin molded body is excellent, and the obtained cured resin molded body has few surface defects.

  The resin mold of the present invention can be used as a resin mold for various molded products, but since the resin mold itself is excellent in productivity, it can be made disposable. Since there is no problem of the curable resin adhering to it and it is excellent in releasability from the cured resin molded body, it is suitable for the production of optical parts that require high accuracy.

  Specific examples of the optical component include an optical lens, a light guide plate, a prism sheet, a Fresnel lens, a lenticular lens, an optical disk substrate and a light transmissive intermediate layer, a magneto-optical disk substrate, an optical card substrate, an optical waveguide, and a contact lens. In particular, a light guide plate, a prism sheet, a Fresnel lens, and a lenticular lens are suitable.

  Hereinafter, although a manufacture example, an Example, and a comparative example are given and this invention is demonstrated more concretely, the scope of the present invention is not limited to these examples. In these examples, unless otherwise specified, parts are based on weight, and pressure is gauge pressure. Moreover, the measuring method of various physical properties is as follows.

(1) Surface roughness The surface roughness of the surface of the resin mold was measured according to JIS-B0601 using a surface roughness meter (Lanck Taylor Hobson Co., Ltd .; Foam Talysurf).
Measurement points, in the case where the outer periphery of the resin mold was ^{X 2 +} Y 2 = ⁶ 2 coordinates (0,0), (3,0), (0,3), (- 3,0), (0, - The average value was defined as the surface roughness.
(2) Contact angle θ with water
Using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd .; DropMaster 300) under the conditions of a temperature of 25 ° C. and a humidity of 50%, the contact angle θ of the resin mold surface with water was measured by the θ / 2 method.
Measurement points, in the case where the outer periphery of the resin mold was ^{X 2 +} Y 2 = ⁶ 2 coordinates (0,0), (3,0), (0,3), (- 3,0), (0, - 3), and the average value was defined as the contact angle θ.
(3) Melt flow rate (MFR)
MFR was measured according to JIS-K7210 (unit: g / 10 min.) Under the conditions of a temperature of 280 ° C. and a load of 2.16 kg using an MFR measuring apparatus (manufactured by Toyo Seiki; SEMI AUTO MELT INDEXER 3A).
(4) Tensile elongation of resin composition Using a tensile tester (manufactured by Shimadzu Corporation; AGS-10 kND), a tensile speed of 5 mm / min. Under the conditions, the tensile elongation (%) of the resin composition was measured according to ASTM-D-638.
(4) Mold separation selectivity Resin-type A / UV curing using a universal tensile / compression testing machine (manufactured by Shinsei Tsushin Kogyo Co., Ltd .; TCM500CR) shown in FIG. 1 under a tensile (peeling) speed of 0.8 mm / second. The mold release selectivity of the resin molded body / resin mold B composite was examined.
Resin mold A / UV curable resin molded body / resin mold B composite is fixed with a suction cup (18 mm in diameter) and a substrate press on a fixing base, and the release claw is raised to form resin mold B and UV curable resin molded body. It was observed whether or not the resin mold A and the UV curable resin molded article were peeled off.
As the number of times the resin mold B peels off from the composite of the resin mold A / UV cured resin molded body / resin mold B in a state where the UV cured resin molded body and the resin mold A are attached, the mold separation selectivity is excellent.
(5) Surface defect of cured resin molded body The resin mold A is peeled from the composite of the UV cured resin molded body 1 / resin mold A obtained in the mold separation selectivity test, and the release surface of the UV cured resin molded body 1 is peeled off. Was observed under a microscope.
Evaluation was made with “◯” indicating no defect and “×” indicating that there was no defect.
(6) The glass transition temperature (Tg) was measured with a differential scanning calorimeter (DSC method).
(7) Unless otherwise specified, the molecular weight was measured as a polyisoprene equivalent value measured by gel permeation chromatography using cyclohexane as a solvent.

[Production Example 1-0]
Under a nitrogen atmosphere, 500 parts of dehydrated cyclohexane was mixed with 0.82 part of 1-hexene, 0.15 part of dibutyl ether, 0.30 part of triisobutylaluminum, and 0.11 part of isobutyl alcohol in a reactor at room temperature. Thereafter, 170 parts of tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene (common name: dicyclopentadiene, hereinafter abbreviated as “DCP”) while maintaining at 45 ° C., 8-ethylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene (hereinafter abbreviated as “ETCD”) 30 parts and tungsten hexachloride (0.7% toluene solution) 80 parts in parallel, continuously over 2 hours. And polymerized. Next, 1.06 part of butyl glycidyl ether and 0.52 part of isopropyl alcohol were added to the polymerization solution to inactivate the polymerization catalyst and stop the polymerization reaction. When the reaction solution containing the obtained ring-opening polymer was analyzed by gas chromatography, the polymerization conversion rate of each monomer was 99.5%.

  Next, 50 parts of cyclohexane is added to 100 parts of the reaction solution containing the obtained ring-opening polymer, and 0.2 part of a diatomaceous earth-supported nickel catalyst (nickel support rate: 58% by weight) is further added as a hydrogenation catalyst. The mixture was pressurized to 5 MPa with hydrogen and heated to 200 ° C. with stirring, and then reacted for 8 hours to obtain a reaction solution containing a hydrogenated DCP / ETCD ring-opening copolymer. The hydrogenation catalyst is removed by filtration, and then the cyclohexane and other volatile components as solvents are removed from the solution at a temperature of 270 ° C. and a pressure of 1 kPa or less using a cylindrical concentrating dryer (manufactured by Hitachi, Ltd.) Next, the hydride was extruded in the form of a strand from the extruder in the molten state, pelletized after cooling to obtain pellets PM. The pelletized ring-opening copolymer hydrogenated product had an Mw of 30,000, a hydrogenation rate of 100%, and a Tg of 100 ° C.

[Production Example 2-0]
100 parts of the ring-opened polymer hydrogenated product (pellet PM) obtained in Production Example 1-0, 0.2 part of a soft polymer (Asahi Kasei Co., Ltd .; Tuftec H1052), an anti-aging agent (Ciba Geigy Co., Ltd .; Irganox) 1010) Add 0.1 part, and with a twin screw kneader (Toshiba Machine TEM-35B, screw diameter 37 mm, L / D = 32, screw rotation speed 250 rpm, resin temperature 240 ° C., feed rate 10 kg / hour) The mixture was kneaded, extruded and pelletized to obtain pellets P0.
The tensile elongation of the obtained resin composition was measured using pellets P0 and found to be 130%.

[Production Example 2-1]
Pellets P1 were obtained in the same manner as in Production Example 2-1, except that 5 parts of glycerin monostearate (manufactured by NOF Corporation; Monogly D) was added as a fatty acid monoester of a polyhydric alcohol. It was 110% when the tensile elongation of the resin composition was measured using the obtained pellet P1.

[Production Example 2-2]
Pellets P2 were obtained in the same manner as in Production Example 2-1, except that 5 parts of glycerol monostearate was changed to 3 parts as a fatty acid monoester of a polyhydric alcohol. When the tensile elongation of the resin composition was measured using the obtained pellet P2, it was 120%.

[Production Example 2-3]
A pellet P3 was obtained in the same manner as in Production Example 2-1, except that 5 parts of glycerin monostearate was changed to 1 part as a fatty acid monoester of a polyhydric alcohol. When the tensile elongation of the resin composition was measured using the obtained pellet P3, it was 127%.

[Production Example 2-4]
A pellet P4 was prepared in the same manner as in Production Example 2-1, except that 5 parts of glycerin monostearate was changed to 10 parts as a fatty acid monoester of a polyhydric alcohol. When the tensile elongation of the resin composition was measured using the obtained pellet P4, it was 105%.

[Production Example 2-5]
A pellet P5 was prepared in the same manner as in Production Example 2-1, except that 5 parts of glycerin monostearate was changed to 22 parts as a fatty acid monoester of a polyhydric alcohol. It was 88% when the tensile elongation of the resin composition was measured using the obtained pellet P5.

[Production Example 2-6]
As in Production Example 2-1, except that 5 parts of a 50:50 mixture of glycerol monostearate and glycerol distearate (Riken Vitamin Co., Ltd .; Riquemar S-200) was used instead of the fatty acid monoester of the polyhydric alcohol. Thus, a pellet P6 was prepared. When the tensile elongation of the resin composition was measured using the obtained pellet P6, it was 115%.

[Production Example 2-7]
A pellet P7 was prepared in the same manner as in Production Example 2-1, except that 5 parts of glycerin tristearate (manufactured by Riken Vitamin Co., Ltd .; Riquemar VT) was used instead of the fatty acid monoester of the polyhydric alcohol. When the tensile elongation of the resin composition was measured using the obtained pellet P7, it was 115%.

[Production Example 2-8]
Pellets P8 were prepared in the same manner as in Production Example 2-1, except that 5 parts of hydrogenated castor oil (Kao Corporation; Kao wax 85P) was used instead of the fatty acid monoester of the polyhydric alcohol. When the tensile elongation of the resin composition was measured using the obtained pellet P8, it was 112%.

[Production Example 2-9]
Pellets P9 were prepared in the same manner as in Production Example 2-1, except that 5 parts of pentaerythritol distearate (manufactured by NOF Corporation; Unistar H476D) was used instead of the fatty acid monoester of the polyhydric alcohol. When the tensile elongation of the resin composition was measured using the obtained pellet P9, it was 112%.

[Production Example 2-10]
A pellet P10 was prepared in the same manner as in Production Example 2-1, except that 5 parts of erucic acid amide (manufactured by Kao Corporation; fatty acid amide) was used instead of the fatty acid monoester of the polyhydric alcohol. When the tensile elongation of the resin composition was measured using the obtained pellet P10, it was 110%.

[Production Example 3]
(Molding of resin mold (B))
Using the pellets obtained in Production Example 2-0, compact disc molding under conditions of a resin temperature of 300 ° C. and a mold temperature of 80 ° C. using an injection molding machine having a compact disc-shaped mold whose surface is mirror finished. Resin mold B (diameter 14 cm, thickness 0.6 mm) was obtained.
The surface roughness of the surface in contact with the resin-type curable resin was 0.1, and the contact angle with water was 95 degrees.

[Example 1]
Using the pellet P1 obtained in Production Example 2-1, an injection molding machine having a compact disk-shaped mold with a mirror-finished surface is compact under the conditions of a resin temperature of 300 ° C. and a mold temperature of 80 ° C. A molding resin mold A1 (diameter 12 cm, thickness 0.6 mm) used in combination with the disk molding resin mold B was molded.
The surface roughness of the surface in contact with the resin-type curable resin and the contact angle with water were measured. The results are shown in Table 1.
Similarly, when the mold was stained visually when 50 resin molds A1 were molded, no stain was observed.

Spin a UV curable resin (Dainippon Ink Co., Ltd .; SD6099) on a resin mold B on which a polytetrafluoroethylene (hereinafter referred to as “PTFE”) resin spacer (inner diameter 119 mm, outer diameter 120 mm, thickness 1 mm) is placed. The resin mold A1 was placed so that air could not enter.
Next, the resin mold A1 / UV cured resin molded body 1 / resin mold B composite 1 was irradiated from the resin mold A1 side with an 80 W / cm high-pressure mercury lamp at a distance of 10 cm and irradiated with ultraviolet rays having an integrated light quantity of 1000 mJ / cm ^2. 1 was obtained. The irradiation time until complete curing was 60 seconds.
Resin mold A1 / UV curable resin molding 2 / resin mold B composite 1-2 was obtained in the same manner as described above except that the following UV curable resin 2 was used as the UV curable resin. The irradiation time until complete curing was 60 seconds.
(Composition of UV curable resin 2)
70 parts of 2,3-dihydroxypropyl methacrylate,
28 parts of methyl methacrylate,
1.5 parts of ethylene glycol dimethacrylate,
2,4,6-trimethylbenzoyldiphenylphosphine oxide 0.5 part

  The mold release selectivity of the obtained composite 1-1 and composite 1-2 and the surface defects of the cured resin molding were measured. The results are shown in Table 1.

[Example 2]
Resin mold A2 (diameter 12 cm, thickness 0.6 mm) was obtained in the same manner as in Example 1 except that pellet P2 was used instead of pellet P1 and the surface treatment of the mold was changed.
The surface roughness of the surface in contact with the resin-type curable resin and the contact angle with water were measured. The results are shown in Table 1.
In the same manner as in Example 1, when the mold was stained visually when 50 resin molds A2 were molded, no dirt was observed.
Further, in the same manner as in Example 1, resin type A2 / UV curable resin molded body 1 / resin type B composite 2-1 and resin type A2 / UV curable resin molded body 2 / resin type B composite 2-2 Got.
The mold release selectivity of the obtained composite 2-1 and composite 2-2 and the surface defects of the cured resin molded body were measured. The results are shown in Table 1.

Example 3
Resin mold A3 (diameter 12 cm, thickness 1.0 mm) was obtained in the same manner as in Example 1 except that pellet P3 was used instead of pellet P1 and the surface treatment of the mold was changed.
The surface roughness of the surface in contact with the resin-type curable resin and the contact angle with water were measured. The results are shown in Table 1.
In the same manner as in Example 1, when the mold was stained visually when 50 resin molds A3 were molded, no stain was observed.
Further, in the same manner as in Example 1, resin type A3 / UV curable resin molded body 1 / resin type B composite 2-1 and resin type A3 / UV curable resin molded body 2 / resin type B composite 3-2. Got.
The mold release selectivity of the obtained composite 3-1 and composite 3-2 and the surface defects of the cured resin molded body were measured. The results are shown in Table 1.

Example 4
Resin mold A4 (diameter 12 cm, thickness 0.6 mm) was obtained in the same manner as in Example 1 except that pellet P4 was used instead of pellet P1 and the surface treatment of the mold was changed.
The surface roughness of the surface in contact with the resin-type curable resin and the contact angle with water were measured. The results are shown in Table 1.
In the same manner as in Example 1, when the mold was stained with 50 resin molds A4, the mold was visually observed. No dirt was observed.
Further, in the same manner as in Example 1, resin type A4 / UV curable resin molded body 1 / resin type B composite 4-1 and resin type A4 / UV curable resin molded body 2 / resin type B composite 4-2 Got.
The mold release selectivity of the obtained composites 4-1 and 4-2 and the surface defects of the cured resin molded body were measured. The results are shown in Table 1.

[Comparative Example 1]
Resin mold A5 (diameter 12 cm, thickness 0.6 mm) was obtained in the same manner as in Example 1 except that pellet P0 was used instead of pellet P1 and the surface treatment of the mold was changed.
The surface roughness of the surface in contact with the resin-type curable resin and the contact angle with water were measured. The results are shown in Table 1.
In the same manner as in Example 1, when the mold was stained visually when 50 resin molds A5 were molded, no dirt was observed.
Further, in the same manner as in Example 1, resin type A5 / UV curable resin molded body 1 / resin type B composite 5-1 and resin type A5 / UV curable resin molded body 2 / resin type B composite 5-2 Got.
The mold release selectivity of the obtained composites 5-1 and 5-2 and the surface defects of the cured resin molded body were measured. The results are shown in Table 1.

[Comparative Example 2]
Resin mold A6 (diameter 12 cm, thickness 0.6 mm) was obtained in the same manner as in Example 1 except that the surface treatment of the mold was changed.
The surface roughness of the surface in contact with the resin-type curable resin and the contact angle with water were measured. The results are shown in Table 1.
In the same manner as in Example 1, when the mold was stained visually when 50 resin molds A6 were molded, no dirt was observed.
Further, in the same manner as in Example 1, resin type A6 / UV curable resin molded body 1 / resin type B composite 6-1 and resin type A6 / UV curable resin molded body 2 / resin type B composite 6-2 Got.
The mold release selectivity of the obtained composite 6-1 and composite 6-2 and the surface defects of the cured resin molded body were measured. The results are shown in Table 1.

[Comparative Example 3]
Resin mold A7 (diameter 12 cm, thickness 2.5 mm) was obtained in the same manner as in Example 1 except that the surface treatment of the mold was changed.
The surface roughness of the surface in contact with the resin-type curable resin and the contact angle with water were measured. The results are shown in Table 1.
In the same manner as in Example 1, when the mold was stained visually when 50 resin molds A7 were molded, no dirt was observed.
Further, in the same manner as in Example 1, resin type A7 / UV curable resin molded body 1 / resin type B composite 7-1 and resin type A7 / UV curable resin molded body 2 / resin type B composite 7-2 Got.
The mold release selectivity of the obtained composite 7-1 and composite 7-2 and the surface defects of the cured resin molded body were measured. The results are shown in Table 1.

[Comparative Example 4]
Resin mold A8 (diameter 12 cm, thickness 0.6 mm) was obtained in the same manner as in Example 1 except that pellet P5 was used instead of pellet P1 and the surface treatment of the mold was changed.
The surface roughness of the surface in contact with the resin-type curable resin and the contact angle with water were measured. The results are shown in Table 1.
Resin mold A8 was cloudy.
In the same manner as in Example 1, when the molds were stained with 50 resin molds A8, the molds were visually stained with pentaerythritol monostearate.
A UV curable resin (manufactured by Dainippon Ink, Inc .; SD6099) is spin coated on a resin mold B on which a PTFE resin spacer (inner diameter 119 mm, outer diameter 120 mm, thickness 1 mm) is placed, and the resin mold prevents air from entering. A8 was carried.
Subsequently, ultraviolet rays with an integrated light quantity of 1000 mJ / cm ² were irradiated from a resin mold A1 side using an 80 W / cm high-pressure mercury lamp at a distance of 10 cm, but the UV curable resin was not cured.
Except for using the UV curable resin 2 as the UV curable resin, ultraviolet rays were irradiated in the same manner as described above, but the UV curable resin was not cured.

[Comparative Example 5]
Resin mold A9 (diameter 12 cm, thickness 0.6 mm) was obtained in the same manner as in Example 1 except that pellet P6 was used instead of pellet P1 and the surface treatment of the mold was changed.
The surface roughness of the surface in contact with the resin-type curable resin and the contact angle with water were measured. The results are shown in Table 1.
In the same manner as in Example 1, when the resin mold A9 of 50 sheets was molded, the mold was visually observed for dirt. Slight dirt was observed.
Further, in the same manner as in Example 1, resin type A9 / UV curable resin molded body 1 / resin type B composite 9-1 and resin type A9 / UV curable resin molded body 2 / resin type B composite 9-2 Got.
The mold release selectivity of the obtained composite 9-1 and composite 9-2 and the surface defects of the cured resin molded body were measured. The results are shown in Table 1.

[Comparative Example 6]
Resin mold A10 (diameter 12 cm, thickness 0.6 mm) was obtained in the same manner as in Example 1 except that pellet P7 was used instead of pellet P1 and the surface treatment of the mold was changed.
The surface roughness of the surface in contact with the resin-type curable resin and the contact angle with water were measured. The results are shown in Table 1.
Resin mold A10 was cloudy.
In the same manner as in Example 1, when the mold was soiled visually when 50 resin molds A10 were molded, the mold was very dirty.
A UV curable resin (manufactured by Dainippon Ink, Inc .; SD6099) is spin coated on a resin mold B on which a PTFE resin spacer (inner diameter 119 mm, outer diameter 120 mm, thickness 1 mm) is placed, and the resin mold prevents air from entering. A10 was placed.
Subsequently, ultraviolet rays having an integrated light quantity of 1000 mJ / cm ² were irradiated from a resin mold A10 side using an 80 W / cm high-pressure mercury lamp at a distance of 10 cm, but the UV curable resin was not cured.
Except for using the UV curable resin 2 as the UV curable resin, ultraviolet rays were irradiated in the same manner as described above, but the UV curable resin was not cured.

[Comparative Example 7]
Resin mold A11 (diameter 12 cm, thickness 0.6 mm) was obtained in the same manner as in Example 1 except that pellet P8 was used instead of pellet P1 and the surface treatment of the mold was changed.
The surface roughness of the surface in contact with the resin-type curable resin and the contact angle with water were measured. The results are shown in Table 1.
Resin mold A11 was cloudy.
In the same manner as in Example 1, when the mold was soiled visually when 50 resin molds A11 were molded, the mold was very dirty.
A UV curable resin (manufactured by Dainippon Ink, Inc .; SD6099) is spin coated on a resin mold B on which a PTFE resin spacer (inner diameter 119 mm, outer diameter 120 mm, thickness 1 mm) is placed, and the resin mold prevents air from entering. A11 was carried.
Subsequently, ultraviolet rays having an integrated light quantity of 1000 mJ / cm ² were irradiated from a resin mold A11 side using an 80 W / cm high-pressure mercury lamp at a distance of 10 cm, but the UV curable resin was not cured.
Except for using the UV curable resin 2 as the UV curable resin, ultraviolet rays were irradiated in the same manner as described above, but the UV curable resin was not cured.

[Comparative Example 8]
Resin mold A12 (diameter 12 cm, thickness 0.6 mm) was obtained in the same manner as in Example 1 except that pellet P9 was used instead of pellet P1 and the surface treatment of the mold was changed.
The surface roughness of the surface in contact with the resin-type curable resin and the contact angle with water were measured. The results are shown in Table 1.
In the same manner as in Example 1, when the mold stains were visually observed when 50 resin molds A12 were molded, the stains were observed.
Further, in the same manner as in Example 1, the resin mold A12 / UV cured resin molded body 1 / resin mold B composite 12-1 and the resin mold A12 / UV cured resin molded body 2 / resin mold B composite 12-2. Got.
The mold release selectivity of the obtained composite 12-1 and composite 12-2 and the surface defects of the cured resin molding were measured. The results are shown in Table 1.

[Comparative Example 9]
Resin mold A13 (diameter 12 cm, thickness 0.6 mm) was obtained in the same manner as in Example 1 except that pellet P10 was used instead of pellet P1 and the surface treatment of the mold was changed.
The surface roughness of the surface in contact with the resin-type curable resin and the contact angle with water were measured. The results are shown in Table 1.
In the same manner as in Example 1, when the mold was stained visually when 50 resin molds A13 were molded, the dirt was observed.
Further, in the same manner as in Example 1, the resin mold A13 / UV cured resin molded body 1 / resin mold B composite 13-1 and the resin mold A13 / UV cured resin molded body 2 / resin mold B composite 13-2. Got.
The mold release selectivity of the obtained composite 13-1 and composite 13-2 and the surface defects of the cured resin molded body were measured. The results are shown in Table 1.

表１から以下のことがわかる。
硬化性樹脂を成形するための樹脂型であって、メルトフローレイトが１〜１５０ｇ／１０ｍｉｎ．の範囲にある脂環構造含有重合体１００重量部に対して３価以上の多価アルコールの脂肪酸モノエステルを０．０１〜２０重量部含有する樹脂組成物（ａ）を成形してなり、該硬化性樹脂と接する面の、表面粗さが０．００１〜１．５μｍの範囲にあり、かつ水との接触角θが１０〜９５度の範囲にある樹脂型は、樹脂型自体の成形の際には、金型と樹脂型の離型性に優れ、かつ金型の汚れが少ないので樹脂型自体の生産性に優れ、かつ得られる樹脂型を用いて硬化性樹脂を成形する際には、硬化樹脂成形体を特定の樹脂型に付着させたまま特定の樹脂型を剥離させることができるので硬化樹脂成形体の生産性に優れ、かつ得られる硬化樹脂成形体の表面欠陥が少ない（実施例１〜４）。
それに対して、３価以上の多価アルコールの脂肪酸モノエステルを含有しない樹脂組成物（ａ）を成型してなる硬化性樹脂用樹脂型であって、該樹脂型の硬化性樹脂と接する面の水との接触角θが１０〜９５度の範囲にない樹脂型は、型離れ選択性に劣る（比較例１）。
樹脂型の硬化性樹脂と接する面の表面粗さが０．００１〜１．５μｍの範囲にない樹脂型は、型離れ選択性に劣り、得られる硬化樹脂成形体の表面に欠陥がある（比較例２〜３）。
脂環構造含有重合体１００重量部に対する３価以上の多価アルコールの脂肪酸モノエステルの含有割合が０．０１〜２０重量部の範囲になく、樹脂型の硬化性樹脂と接する面の水との接触角θが１０〜９５度の範囲にない樹脂型は、樹脂型自体の成形の際には金型の汚れが多く、得られた樹脂型を用いて硬化性樹脂を硬化させることができなかった（比較例４）。
３価以上の多価アルコールの脂肪酸エステルが３価以上の多価アルコールの脂肪酸モノエステルでない樹脂型は、樹脂型自体の成形の際には金型の汚れが多く、型離れ選択性に劣り、得られる硬化樹脂成形体の表面に欠陥があったり、硬化性樹脂を硬化させることができなかった（比較例５〜９）。

Table 1 shows the following.
A resin mold for molding a curable resin having a melt flow rate of 1 to 150 g / 10 min. A resin composition (a) containing 0.01 to 20 parts by weight of a trihydric or higher polyhydric alcohol fatty acid monoester with respect to 100 parts by weight of the alicyclic structure-containing polymer in the range of A resin mold having a surface roughness in the range of 0.001 to 1.5 μm and a contact angle θ with water in the range of 10 to 95 degrees of the surface in contact with the curable resin is the molding of the resin mold itself. In this case, the mold and the resin mold are excellent in releasability, and the mold is less contaminated, so the resin mold itself is excellent in productivity, and when the curable resin is molded using the obtained resin mold Because the specific resin mold can be peeled off while the cured resin molded body is attached to the specific resin mold, the cured resin molded body is excellent in productivity, and the resulting cured resin molded body has few surface defects. Examples 1-4).
On the other hand, a resin mold for a curable resin formed by molding a resin composition (a) that does not contain a fatty acid monoester of a trihydric or higher polyhydric alcohol, the surface being in contact with the curable resin of the resin mold A resin mold having a contact angle θ with water in the range of 10 to 95 degrees is inferior in mold separation selectivity (Comparative Example 1).
Resin molds whose surface roughness in contact with the curable resin of the resin mold is not in the range of 0.001 to 1.5 μm are inferior in mold release selectivity, and the surface of the resulting cured resin molded product has defects (comparison) Examples 2-3).
The content ratio of the fatty acid monoester of the trihydric or higher polyhydric alcohol with respect to 100 parts by weight of the alicyclic structure-containing polymer is not in the range of 0.01 to 20 parts by weight, and the water in contact with the resin-type curable resin Resin molds whose contact angle θ is not in the range of 10 to 95 degrees are often contaminated with molds when molding the resin mold itself, and the curable resin cannot be cured using the obtained resin mold. (Comparative Example 4).
A resin mold in which a fatty acid ester of a trihydric or higher polyhydric alcohol is not a trihydric or higher polyhydric alcohol fatty acid monoester has a large amount of mold contamination during molding of the resin mold itself, and has poor mold release selectivity. There were defects on the surface of the resulting cured resin molded body, or the curable resin could not be cured (Comparative Examples 5 to 9).

The resin mold of the present invention has excellent mold releasability between the mold and the resin mold when molding the resin mold itself, and is excellent in productivity of the resin mold itself because there is little dirt on the mold.
In addition, when the curable resin is molded using the resin mold of the present invention, the adhesive strength between the resin mold and the obtained cured resin molded body is appropriate, so the cured resin molded body is attached to a specific resin mold. Since the specific resin mold can be peeled as it is, the productivity of the cured resin molded body is excellent, and the obtained cured resin molded body has few surface defects.
Therefore, the resin mold of the present invention is suitable as a disposable resin mold for a cured resin molded body that requires high surface accuracy.

It is sectional drawing which shows the state which peels the resin mold A from the composite_body | complex of resin mold A / UV cured resin molding / resin mold B in a mold separation selectivity test.

Explanation of symbols

1: Resin mold B
2: Cured resin molding 3: Resin mold A
4: Substrate holder 5: Peel for peeling 6: Fixing base 7: Suction cup (diameter 18 mm)
8: Spacer 9: Direction of movement of claw for peeling

Claims (8)

A resin mold for molding a curable resin,
Melt flow rate is 1-150 g / 10 min. A resin composition (a) containing 0.01 to 20 parts by weight of a trihydric or higher polyhydric alcohol fatty acid monoester with respect to 100 parts by weight of the alicyclic structure-containing polymer in the range of
Of the surface in contact with the curable resin,
The surface roughness is in the range of 0.001 to 1.5 μm,
And a resin mold having a contact angle θ with water in the range of 10 to 95 degrees. The resin mold according to claim 1, wherein the fatty acid monoester of the polyhydric alcohol is glycerin monostearate. The resin mold according to claim 1 or 2, wherein the tensile elongation of the resin composition (a) is 40% or more. The resin mold according to any one of claims 1 to 3, wherein a thickness of the resin mold is in a range of 0.5 to 2 mm. The resin mold (resin mold (A)) according to any one of claims 1 to 4 and a melt flow rate of 1 to 150 g / 10 min. A resin composition comprising an alicyclic structure-containing polymer in the range of the above, wherein the content ratio of a fatty acid monoester of a trihydric or higher polyhydric alcohol relative to the alicyclic structure-containing polymer is (1) Resin mold (B) formed by molding less resin composition (b) than a)
A composite resin mold. A cured resin molded body formed by using the resin mold according to claim 1. A step of curing and molding a curable resin in a space formed by the resin mold (A) according to any one of claims 1 to 4 and the resin mold (B) according to claim 5, and an obtained cured resin A method for producing a cured resin molded body comprising a step of peeling the cured resin molded body from the resin mold (A) after peeling the molded body from the resin mold (B) in a state where the molded body is adhered to the resin mold (A). A cured resin molded product obtained by the production method according to claim 7.

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