TWI576374B - And a method for producing a hardened resin molded article - Google Patents

Description

Method for producing cured resin molded article

The present invention relates to a method for producing a cured resin molded article using a curable resin composition. Specifically, the method for producing a cured resin molded article having a three-dimensional shape suitable for use as an optical member for transparency, heat resistance, and surface hardness is used.

Conventionally, various substrates for display elements such as a liquid crystal display, an organic EL display, and a touch panel, a frame as a constituent member, a front panel, an optical lens, and the like are mainly made of glass, but they have been discussed so as to be lightweight and difficult to be used. Plastics with characteristics such as rupture replace the glass, and various thicknesses of plastic are proposed depending on the characteristics.

PET (Polyethylene Terephthalate; polyethylene terephthalate) or PEN (Polyethylene Naphthalate; polyethylene naphthalate), polyester, polycarbonate (PC), polymethyl methacrylate (PMMA), A thermoplastic plastic such as an amorphous polyolefin (amorphous PO) is excellent in light weight, is not easily broken, and is bendable. However, although these plastics are excellent in transparency, they are insufficient in heat resistance and have a low surface hardness. Therefore, it is necessary to provide a hard coat layer depending on the application.

On the other hand, since the curable resin has a crosslinked structure, it has high heat resistance and excellent surface hardness. In particular, a molded article using an allyl ester-based resin is excellent in heat resistance, transparency, optical properties, and mechanical properties, and is known as a substrate for an optical lens or a transparent conductive substrate (Japanese special) JP-A-2001-114850 (Patent Document 1) and JP-A-2007-299739 (WO2007/117030) (Patent Document 2)).

In recent years, there has been an increase in the demand for thinning of the display device, and there has been an increase in the demand for thinning of a film or sheet of a raw material. For the formation of a film or a sheet of an allyl ester resin, there is known a method of forming a film by photohardening or heat hardening (JP-A-2009-197102 (US2009/209718) (Patent Document 3)). However, the film or sheet obtained in these molding methods has a flat shape, and a molded article having a curved shape or a three-dimensional shape is not described. In addition, in recent years, front panels or frames of various shapes such as mobile phones or smart phones, tablet computers, and the like have been proposed, and there is a demand for materials which are transparent and heat resistant, have high surface hardness, and are curved or three-dimensional shapes. However, there are still no materials that can satisfy such characteristics.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2001-114850

[Patent Document 2] Japanese Laid-Open Patent Publication No. 2007-299739 (WO2007/117030)

[Patent Document 3] Japanese Laid-Open Patent Publication No. 2009-197102 (US2009/209718)

An object of the present invention is to provide a method for producing a molded article which is suitable for use as an optical member and which is excellent in heat resistance and surface hardness and which has a curved shape or a three-dimensional shape.

The present inventors have intensively studied to solve the problem, and as a result, it has been found that the semi-cured product of the allyl ester resin composition can be used for secondary processing to achieve the object, and thus the present invention has been completed.

That is, the present invention relates to the following items [1] to [7].

[1] A method for producing a cured resin molded article, characterized in that after semi-curing a film or sheet of an allyl ester resin composition, the semi-cured film or sheet is formed into a desired three-dimensional shape and maintained. Secondary hardening is performed in the state of the aforementioned shape.

[2] A method for producing a cured resin molded article, characterized in that after the film or sheet of the allyl ester resin composition is semi-cured, another film or sheet is bonded to the semi-cured film or sheet, It is formed into a desired three-dimensional shape, and is subjected to secondary hardening while maintaining the aforementioned shape.

[3] The method for producing a cured resin molded article according to the above item 1 or 2, wherein the semi-cured film or sheet has a colloid fraction of 20 to 90%.

[4] The method for producing a cured resin molded article according to any one of the items 1 to 3, wherein the allyl ester resin composition contains a photopolymerization initiator and a thermal polymerization initiator, and the light is irradiated to carry out the aforementioned The semi-curing of the allyl ester resin composition is subjected to secondary hardening by heating.

[5] The method for producing a cured resin molded article according to the above item 2, wherein The other film or sheet is selected from the group consisting of allyl ester resin, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polymethyl methacrylate, cycloolefin polymer, triacetic acid. Cellulose, polyimine, polyaramid, polyether oxime, siloxane polymer, fluoropolymer, amorphous polyolefin, unsaturated polyester resin, vinyl ester resin, epoxy A film or sheet of resin of resin and urethane acrylate resin.

[6] The method for producing a cured resin molded article according to any one of the items 1 to 5, wherein the secondary hardening is performed by heating in a mold.

[7] The method for producing a cured resin molded article according to any one of the items 1 to 5, wherein the allyl ester resin composition contains an allyl ester oligomer having a general formula (2) The base of the representation is a terminal group, and has a structure represented by the general formula (3) as a constituent unit; (wherein R ³ represents a hydrogen atom or a methyl group, and A ² represents one or more organic residues having an alicyclic structure and/or an aromatic ring structure derived from a dicarboxylic acid); (wherein A ³ represents one or more organic residues having an alicyclic structure and/or an aromatic ring structure derived from a dicarboxylic acid, and X represents one or more organic residues derived from a polyhydric alcohol; From the ester bond, a branching structure having a group represented by the above general formula (2) as a terminal group and a structure represented by the above general formula (3) as a constituent unit is formed.

According to the present invention, it is possible to manufacture a molded article which is transparent to a mobile phone, a tablet PC, or the like and which is excellent in surface hardness and heat resistance and which is three-dimensional and has a curved shape.

1‧‧‧film or sheet of resin composition

2 (2a, 2b) ‧ ‧ mold

3‧‧‧ hardened resin molded article

Figs. 1(a) to 1(d) are diagrams each showing an example of a three-dimensionally shaped cured resin molded article obtainable by the method of the present invention.

Fig. 2 is a flow chart showing the steps of an example of the manufacturing method of the present invention.

Fig. 3 is a photograph of a cylindrical cured resin molded article obtained in Example 1.

Fig. 4 is a view showing the formation of a cylindrical hardened resin obtained in Example 2. Photo of the product.

Fig. 5 is a photograph of a cylindrical molded resin molded article obtained in Example 3.

Fig. 6 is a photograph of a cylindrical cured resin molded article obtained in Example 4.

Fig. 7 is a photograph of a cylindrical molded resin molded article obtained in Example 5.

Fig. 2 is a view showing an example of an example of a method for producing a cured resin molded article of the present invention. In this example, ultraviolet rays (UV) are irradiated onto the film or sheet (1) of the allyl ester resin composition (step a) to prepare a semi-hardened film or sheet (step b), and the mold (2a, 2b) is used. The film or sheet is formed into a desired shape (step c), heated in a mold to perform secondary hardening (step d), and then demolded to obtain a cured resin molded article (3), and the end portion is cut as necessary (step e ).

The method for producing a cured resin molded article of the present invention is characterized in that a film or sheet of a semi-cured (semi-cured) film comprising an allyl ester resin composition containing a photopolymerization initiator and a thermal polymerization initiator is formed into a desired The three-dimensional shape is hardened by heating while maintaining the shape. The details are as follows.

[Allyl ester resin]

The semi-hardened allyl ester resin composition used in the present invention The allyl ester resin is one of thermosetting resins.

In general, the term "allyl ester resin" means a prepolymer (including an oligomer or an additive, a reactive monomer (also referred to as "reactive diluent"), a solvent) before curing. In the present specification, "allyl ester resin" means a cured product, and "allyl ester resin composition" means a prepolymer before curing.

[Allyl ester resin composition]

The allyl ester resin composition used in the present invention contains an allyl group or a methallyl group (hereinafter sometimes referred to as (meth)allyl group. (Methyl) allyl alcohol is also the same) The compound with the ester structure serves as a constituent of the main hardening component.

A compound having a (meth)allyl group and an ester structure can be obtained by: (1) a compound containing a (meth)allyl group and a hydroxyl group (to simplify the performance, the following is collectively referred to as "(meth)allyl alcohol". Esterification reaction with a compound containing a carboxyl group, (2) esterification reaction of a compound containing a (meth)allyl group and a carboxyl group with a compound containing a hydroxyl group, or (3) by (meth)allyl alcohol and The esterified product of a dicarboxylic acid is obtained by transesterification of a polyhydric alcohol. When the compound having a carboxyl group is a polyester oligomer of a dicarboxylic acid and a diol, only the terminal may be an ester with (meth)allyl alcohol.

Specific examples of the ester compound composed of the (meth)allyl alcohol and the dicarboxylic acid include at least one compound selected from the group consisting of the compounds represented by the general formula (1). This compound may be included as a reactive diluent (reactive monomer) in addition to the raw material of the allyl ester oligomer described later. The allyl ester resin composition of the invention.

(R ¹ and R ² each independently represent any one of a hydrogen atom and a methyl group, and A ¹ represents one or more organic residues having an alicyclic structure and/or an aromatic ring structure derived from a dicarboxylic acid).

A ¹ in the general formula (1) is preferably the same as A ² and A ³ in the general formula (2) and the general formula (3) described later.

a compound having a (meth)allyl group and an ester structure as a main hardening component of the allyl ester resin composition, preferably having an allyl group and/or a methallyl group as a terminal group, and having a polyol and An allyl ester compound having an ester structure formed by a dicarboxylic acid (hereinafter referred to as "allyl ester oligomer"). The allylate resin composition may contain, as a component other than the above-mentioned compound, a curing agent, a reactive diluent, another monomer, an additive, and other radically reactive resin component which will be described later.

[Allyl ester oligomer]

The main component of the allyl ester resin composition used in the present invention preferably has a group represented by the general formula (2) as a terminal group, and has a general The structure represented by the formula (3) serves as a constituent unit of the allyl ester oligomer.

(wherein R ³ represents a hydrogen atom or a methyl group, and A ² represents one or more organic residues having an alicyclic structure and/or an aromatic ring structure derived from a dicarboxylic acid), (wherein A ³ represents one or more organic residues having an alicyclic structure and/or an aromatic ring structure derived from a dicarboxylic acid, and X represents one or more organic residues derived from a polyhydric alcohol; From the ester bond, a branching structure having a group represented by the above general formula (2) as a terminal group and a structure represented by the above general formula (3) as a constituent unit is formed.

In the above allyl ester oligomer, the number of terminal groups represented by the general formula (2) is at least two or more, but when the X represented by the general formula (3) has a branching structure, it is three or more. . In this case, a plurality of R ³ groups are present in each terminal group, and each of these R ³ does not have to be of the same type, and may have a structure in which one terminal is an allyl group and the other terminal is a methyl allyl group. Further, all of the terminals need not be an allyl group or a methallyl group, and the portion may be a non-polymerizable group such as a methyl group or an ethyl group insofar as the curability is not impaired. The structure represented by A ² is also the same, and each terminal group may be different. For example, A ² at one end is a benzene ring and the other end is a cyclohexane ring structure.

A ² in the general formula (2) is one or more organic residues having an alicyclic structure and/or an aromatic ring structure derived from a dicarboxylic acid. The moiety derived from the dicarboxylic acid is represented by a carbonyl structure adjacent to A ² . Therefore, the moiety of A ² represents a benzene skeleton or a cyclohexane skeleton.

The dicarboxylic acid derived from the A ² structure is not particularly limited, and from the viewpoint of easiness of obtaining a raw material, terephthalic acid, isophthalic acid, phthalic acid, and 1,4-cyclohexane are preferred. Carboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, diphenyl-m, m'- Dicarboxylic acid, diphenyl-p,p'-dicarboxylic acid, diphenylketone-4,4'-dicarboxylic acid, terephthalic acid, p-carboxyphenylacetic acid, methyl terephthalic acid, tetra Chlorophthalic acid, particularly preferably terephthalic acid, isophthalic acid, phthalic acid, 1,4-cyclohexanedicarboxylic acid. Among them, those having 1,4-cyclohexanedicarboxylic acid having no aromatic ring in the molecule are preferred from the viewpoint of light resistance, and in applications requiring high transparency, 1,4 are preferably used. - cyclohexanedicarboxylic acid.

Further, in addition to the dicarboxylic acid derived from the A ² structure, maleic acid, fumaric acid, itaconic acid, citraconic acid, and descending can be used within the range not detracting from the effects of the present invention. An acyclic dicarboxylic acid (in the case of reaction) of borneol dianhydride or chlorinic anhydride.

The structural unit represented by the general formula (3) needs to have at least one of the allyl ester oligomers, and by repeating the structure, the molecular weight of the entire allyl ester oligomer is increased to some extent. It is preferable to increase the workability with an appropriate viscosity and to improve the toughness of the cured product. However, when the molecular weight is too large, the molecular weight between the crosslinking points of the cured product also becomes too large, and the glass transition temperature (Tg) is lowered, and there is a fear that heat resistance is lowered. It is important to adjust to the proper molecular weight depending on the application. The weight average molecular weight of the allyl ester oligomer is preferably from 500 to 200,000, more preferably from 1,000 to 100,000.

Further, A ³ in the general formula (3) is one or more organic residues having an alicyclic structure and/or an aromatic ring structure derived from a dicarboxylic acid, and an example of the definition and preferred compound is a general formula. The A ² in (2) is the same.

The X in the general formula (3) represents one or more organic residues derived from a polyol. The polyol is a compound having two or more hydroxyl groups, and X itself represents a skeleton portion other than the hydroxyl group of the polyol. The hydroxyl group in the polyol may be at least two, and therefore, when the polyol to be a raw material is trivalent or higher, that is, when the hydroxyl group is three or more, an unreacted hydroxyl group may be present. The carbon number of the polyol is preferably from 2 to 20.

In a specific example of the polyol having 2 to 20 carbon atoms, examples of the divalent alcohol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butylene glycol, 1,4-butanediol, and 1,5. - pentanediol, neopentyl glycol, hexamethylene glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 2-methyl-1,3-propanediol, 3-methyl- 1,5-pentanediol, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, ethylene oxide adduct of bisphenol-A, propylene oxide adduct of bisphenol-A And hydrogenated bisphenol A, 2,2-[4-(2-hydroxyethoxy)-3,5-dibromophenyl]propane, and the like.

Further, specific examples of the trivalent or higher polyhydric alcohol include glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, and dipentaerythritol. A mixture of two or more kinds of polyols can be used for this purpose. Further, it is not limited to the above specific examples.

The structural unit represented by the general formula (3) in the allyl ester oligomer, which may repeat the same structural unit or contain different structural units. That is, the allyl ester oligomer can be in a copolymerized form. At this time, a plurality of X groups are present in one allyl ester oligomer. For example, one of X may be a residue derived from propylene glycol, and the other X may be a structure derived from a residue of trimethylolpropane. At this time, the allyl ester oligomer forms a branch on the portion of the residue of trimethylolpropane. A ^{3 can} also exist in multiples. The following is a structural formula in which R ³ is an allyl group, A ² and A ³ are residual groups derived from isophthalic acid, and X is propylene glycol and trimethylolpropane.

[Method for producing allyl ester oligomer]

The allyl ester oligomer used in the present invention can be obtained by transesterification of an allyl ester monomer of a polyvalent carboxylic acid with a polyol having 2 to 6 hydroxyl groups. Allyl ester monomer of polycarboxylic acid, polycarboxylic acid and (meth) allylic An ester of an alcohol, particularly preferably an allyl ester monomer of a dicarboxylic acid. Specific examples thereof include diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl 2,6-naphthalene dicarboxylate, and 1,2-cyclohexane. Diallyl alkanedicarboxylate, diallyl 1,3-cyclohexanedicarboxylate, diallyl 1,4-cyclohexanedicarboxylate, endomethylenetetrahydrophthalic acid Allyl ester, diallyl methyltetrahydrophthalate, diallyl adipate, diallyl succinate, diallyl maleate, and the like. These allyl ester monomers may be used in combination of two or more kinds as necessary. Further, it is not limited to the above specific examples.

As the polyol, the aforementioned polyol derived from the X structure can be used.

In order to obtain an allyl ester oligomer having a (meth)allyl ester group at the terminal, the use ratio of these is such that a smaller number of hydroxyl groups of the polyol must be used than the carboxyl group of the dicarboxylic acid.

The transesterification catalyst used in the present invention may be a conventionally known transesterification catalyst, and particularly preferred are alkali metals, alkaline earth metals and oxides thereof, and weak acid salts, Mn, U, and Zn. , organic oxides of oxides, hydroxides, inorganic acid salts, alcoholates, organic acid salts, dibutyltin oxide, dioctyltin oxide, dibutyltin dichloride, etc. of Cd, zr, Pb, Ti, Co and Sn Compounds, etc. Preferred among them are dibutyltin oxide and dioctyltin oxide.

This amount varies depending on the activity of the catalyst, and an amount capable of distilling allyl alcohol at an appropriate rate should be used. In general, the allyl ester monomer of the polyvalent carboxylic acid is preferably used in an amount of 0.0001 to 1% by mass, particularly preferably 0.001 to 0.5% by mass.

The reaction temperature in the production step is not particularly limited, and is preferably located. The range of 120 to 230 ° C is particularly preferably in the range of 140 to 200 ° C.

In order to promote the progress of the reaction, it is necessary to carry out the reaction under reduced pressure or to remove the derived allyl alcohol to the outside of the reaction system using a suitable solvent.

A specific production method of the allyl ester oligomer is described, for example, in Japanese Patent Publication No. Hei 6-74239 (US Pat. No. 4,495,451).

[hardener]

A hardener can be used for the allyl ester resin composition used in the present invention. The curing agent which can be used is not particularly limited, and those which are generally used as a curing agent for a polymerizable resin can be used. From the standpoint of the initiation of polymerization of the allyl group, it is preferred to add a radical polymerization initiator. Examples of the radical polymerization initiator include an organic peroxide, a photopolymerization initiator, an azo compound, and the like.

As the organic peroxide, a general known person such as dioxane, perylene peroxide, hydrogen peroxide, ketone peroxide or peroxyester can be used. Specific examples thereof include benzamidine peroxide and 1,1. - bis(tertiary butylperoxy)cyclohexane, 2,2-bis(4,4-dibutylperoxycyclohexyl)propane, tert-butylperoxy-2-ethylhexanoic acid Ester, 2,5-dimethyl 2,5-di(tri-butylperoxy)hexane, 2,5-dimethyl 2,5-bis(benzhydrylperoxy)hexane, Tert-butyl butyl peroxybenzyl acrylate, tertiary butyl cumene peroxide, p-methyl hydroperoxide, tertiary butyl hydroperoxide, cumene hydroperoxide, dicumyl peroxide, Di(tributyl) peroxide and 2,5-dimethyl-2,5-dibutylperoxyhexyne-3 and the like.

Further, examples of the photopolymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, diphenyl ketone, and 2 -methyl-1-(4-methylthiophenyl)-2-morpholinpropane-1,2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone -1,2-hydroxy-2-methyl-1-phenylpropan-1-one and 2,4,6-trimethylbenzimidium diphenylphosphine oxide.

Examples of the azo compound include 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) and 2,2'-azobis(2,4-dimethylpentyl). Nitrile), dimethyl 2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclo) Hexane-1-carbonylnitrile), 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide], 1-[(1-cyano-1-methylidene) Azo]carbamamine, 2,2'-azobis(N-butyl-2-methylpropionamide), 2,2'-azobis(N-cyclohexyl-2-methyl Propylamine) and the like.

These radical polymerization initiators may be used alone or in combination of two or more. When the semi-curing of the film or sheet of the allyl ester resin composition is carried out by irradiation with an active energy ray such as UV, the reaction control which is stopped at the time of semi-hardening can be easily performed. Further, a thermosetting radical polymerization initiator such as an organic peroxide is suitable for the subsequent secondary hardening and post-hardening thereafter. Therefore, it is especially preferable to combine two or more kinds of hardeners, and it is especially preferable to combine a photopolymerization initiator and a thermal polymerization initiator.

The amount of the curing agent to be added is not particularly limited, and is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the radical polymerization component in the allyl ester resin composition. When the compounding amount of the hardener is less than 0.1 part by mass, it is difficult to obtain a sufficient hardening speed, and further, when the compounding amount exceeds 10 parts by mass, the final cured product becomes brittle, and When the mechanical strength is lowered.

[reactive monomer]

In the allyl ester resin composition used in the present invention, a reactive monomer may be added for the purpose of controlling the curing reaction rate, adjusting the viscosity (improving the workability), improving the crosslinking density, and adding a function. Reactive diluent). The reactive monomer is not particularly limited, and various ones can be used. However, in order to react with the allyl ester oligomer, a monomer having a radically polymerizable carbon-carbon double bond such as a vinyl group or an allyl group is preferred. . For example, an unsaturated fatty acid ester, an aromatic vinyl compound, a saturated fatty acid, a vinyl ester of an aromatic carboxylic acid, its derivative, a crosslinkable polyfunctional monomer, etc. are mentioned. When a crosslinkable polyfunctional monomer is used, the crosslinking density of the cured product can also be controlled. Preferred specific examples of such reactive monomers are shown below.

Examples of the unsaturated fatty acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and (meth)acrylic acid. An alkyl (meth)acrylate such as octyl ester, dodecyl (meth)acrylate, octadecyl (meth)acrylate, cyclohexyl (meth)acrylate or methylcyclohexyl (meth)acrylate; Phenyl (meth)acrylate, benzyl (meth)acrylate, 1-naphthyl (meth)acrylate, fluorophenyl (meth)acrylate, chlorophenyl (meth)acrylate, cyanide (meth)acrylate Acrylic aromatic esters such as phenyl ester, methoxy (meth) acrylate and diphenyl (meth) acrylate; fluoromethyl (meth) acrylate and chloromethyl (meth) acrylate (methyl) a haloalkyl acrylate; Further, glycidyl (meth)acrylate, alkyl (meth)acrylate, and α-cyanoacrylate.

Examples of the aromatic vinyl compound include styrene, α-methylstyrene, chlorostyrene, styrenesulfonic acid, 4-hydroxystyrene, and vinyltoluene.

Examples of the vinyl ester of a saturated fatty acid or an aromatic carboxylic acid and derivatives thereof include vinyl acetate, vinyl propionate, and vinyl benzoate.

Examples of the crosslinkable polyfunctional monomer include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and di(methyl). ) tetraethylene glycol acrylate, tripropylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-butylene glycol di(meth)acrylate, two ( 1,5-pentanediol methyl methacrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, oligoester di(meth)acrylate , poly(butadienyl)(meth)acrylate, 2,2-bis(4-(methyl)propenyloxyphenyl)propane, and 2,2-bis(4-ω-(methyl)propene oxime Di(meth)acrylate such as oxytriethoxy)phenyl)propane; diallyl phthalate, diallyl isophthalate, dimethylallyl isophthalate, Diallyl terephthalate, triallyl trimellitate, diallyl 2,6-naphthalene dicarboxylate, diallyl 1,5-naphthalene dicarboxylate, 1,4-xylene Aromatic carboxylic acid diallyl esters such as allyl dicarboxylate and diallyl 4,4'-diphenyldicarboxylate; diallyl 1,4-cyclohexanedicarboxylate a difunctional crosslinkable monomer such as diallyl 1,2-cyclohexanedicarboxylate, diallyl 1,3-cyclohexanedicarboxylate or divinylbenzene; tris(meth)acrylic acid Trimethylolethane ester, trimethylolpropane tris(meth)acrylate, three Pentaerythritol (meth)acrylate, trimeric isocyanate tris(meth)acrylate, tris(methyl)allyl cyanurate, triallyl trimellitate and diallyl clonate a trifunctional crosslinkable monomer such as a trifunctional group; and a tetrafunctional crosslinkable monomer such as tetrakis(meth)acrylic acid pentaerythritol ester.

The above-mentioned reactive monomers may be used singly or in combination of two or more kinds. The amount of the resin component of the reactive monomer is not particularly limited, and is preferably from 1 to 1,000 parts by mass, particularly preferably from 2 to 500 parts by mass, per 100 parts by mass of the allyl ester oligomer. It is 5 parts by mass to 100 parts by mass. When the amount of the reactive monomer is less than 1 part by mass, the effect of lowering the viscosity is small, and the workability is deteriorated. When a polyfunctional monomer is used as the reactive monomer, the crosslinking density is lowered, and heat resistance may be caused. Become insufficient. Further, when the amount is more than 1,000 parts by mass, the excellent transparency of the allyl ester resin itself may not be exhibited, or the mechanical strength from the allyl ester resin may be lowered.

[Radical Reactive Resin Component]

The allyl ester resin composition used in the present invention may contain a radical reactive resin component for the purpose of improving various properties. Examples of such a resin component include an unsaturated polyester resin and a vinyl ester resin.

The unsaturated polyester resin is a condensation product formed by esterification reaction of a polyhydric alcohol with an unsaturated polyprotic acid (and a saturated polyprotic acid as necessary), and is required to be dissolved in a polymerizable unsaturated compound such as styrene. For example, the "Polyester Resin Manual" Resin ) Journal of the Industrial News Agency, issued in 1988, pages 16 ~ page 18 and page 29 ~ page 37 and other resins. The unsaturated polyester resin can be produced by a generally known method.

A vinyl ester resin, also called epoxy (meth)acrylate, generally means a compound having an epoxy group represented by an epoxy resin, and a polymerizable unsaturated group such as (meth)acrylic acid. a resin having a polymerizable unsaturated group formed by a ring-opening reaction of a carboxyl group of a carboxyl compound, or a polymerizable group having a carboxyl group by a compound having a carboxyl group or a glycidyl (meth)acrylate A resin having a polymerizable unsaturated group formed by a ring-opening reaction of an epoxy group of an unsaturated compound. Details such as "Polyester Resin Manual" Resin The Nikkan Kogyo Shimbun, published in 1988, pages 336 to 357, etc., can be manufactured by a generally known method.

Examples of the epoxy resin which is a raw material of the vinyl ester resin include bisphenol A diglycidyl ether and a high molecular weight homolog thereof, a glycidyl ether of a bisphenol A alkylene oxide adduct, bisphenol F diglycidyl ether, and The high molecular weight homologue, the glycidyl ether of the bisphenol F alkylene oxide adduct, the phenolic polyglycidyl ether, and the like.

The above-mentioned radical reactive resin component may be used singly or in combination of two or more kinds. The amount of the radically reactive resin component to be used is not particularly limited, and is preferably from 1 to 1,000 parts by mass, particularly preferably from 2 to 500 parts by mass, per 100 parts by mass of the allyl ester oligomer, particularly preferably 5 to 100 parts by mass. When the amount of the reactive monomer is less than 1 part by mass, the effect of improving the mechanical strength from the radical reactive resin component is small, and the workability or moldability may be deteriorated. Also, when the amount exceeds When it is 1000 parts by mass, the heat resistance of the allyl ester resin itself may not be exhibited.

[additive]

The allylate resin composition used in the present invention is intended to improve hardness, strength, formability, durability, and water resistance, and may be added with an antioxidant, a UV absorber, a lubricant, an antifoaming agent, and a flattening agent as necessary. Additives such as a chemical agent, a mold release agent, a water repellent agent, a flame retardant, a low shrinkage agent, and a crosslinking auxiliary agent.

The antioxidant is not particularly limited and can be used by a general user. Among them, a phenol-based antioxidant or an amine-based antioxidant which is preferably a free-chain inhibitor is preferable, and a phenol-based antioxidant is particularly preferred. Examples of the phenolic antioxidant include 2,6-tert-butyl-p-cresol, 2,6-tris-butyl-4-ethylphenol, and 2,2'-methylenebis(4-methyl-). 6-tertiary butyl phenol) and 1,1,3-tris(2-methyl-4-hydroxy-5-tributyl phenol) butane.

The ultraviolet absorber is not particularly limited and can be used by a general user. Among them, a diphenylketone-based ultraviolet absorber, a benzotriazole-based ultraviolet absorber, and a cyanoacrylate-based ultraviolet absorber are preferable, and a diphenylketone-based ultraviolet absorber is particularly preferred. Examples of the diphenyl ketone-based ultraviolet absorber include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole and 2-(2'-hydroxy-5'-butylphenyl)benzene. And triazole and 2-(2'-hydroxy-3'-tertiary butylphenyl)benzotriazole and the like.

The lubricant is not particularly limited and can be used by a general user. Among them, a metal soap-based lubricant, a fatty acid ester-based lubricant, an aliphatic hydrocarbon-based lubricant, and the like are preferable, and a metal soap-based lubricant is particularly preferable. Metal soap lubricants, can be listed Examples include barium stearate, calcium stearate, zinc stearate, barium stearate, magnesium stearate, and aluminum stearate. These can also be used as a composite.

Examples of the antifoaming agent include organic antifoaming agents such as polyethers and surfactants, and polyoxynoxy defoaming agents.

Examples of the planarizing agent include a polyfluorene-based planarizing agent and an acrylic planarizing agent.

Examples of the release agent include a polyfluorene-based release agent, a fluorine-based release agent, a wax-based release agent, a polyvinyl alcohol-based release agent, and a stearic acid metal salt-based release agent.

Examples of the water repellent include a polyfluorinated water repellent, a fluorine water repellent, and a wax water repellent.

Examples of the flame retardant include a phosphorus-based flame retardant such as trimethyl phosphate, an inorganic flame retardant such as aluminum hydroxide, and a halogen-free organic compound-based flame retardant such as melamine cyanurate.

Examples of the low shrinkage agent include organic polymer-based low shrinkage agents such as polystyrene, polyvinyl acetate, and styrene-vinyl acetate block copolymer.

Examples of the crosslinking assistant include triallyl triallyl isocyanate, trimethylisocyanate trimethylallyl ester, and triallyl cyanurate.

These additives are not limited to the above specific examples, and any one may be added within a range not inhibiting the object or effect of the present invention.

[Manufacturing method of film or sheet of semi-hardened allyl ester resin composition]

a semi-hardened film or sheet of an allyl ester resin used in the present invention, The allyl ester resin composition is stretched on a substrate of another film or sheet, a flat plate or the like, and heated to obtain a gel composition by heating the resin composition or irradiating with an active energy ray. At the time of heating or activation of the energy ray, the substrate-shaped resin composition can be coated with a cover film or sheet.

The "semi-hardened" state in the present invention means that a part of a monomer or an allyl ester oligomer contained in a resin composition undergoes a crosslinking reaction to form a three-dimensional network structure, and an unreacted structure remains in the mesh structure. The state of the reaction component and plastic deformation. The degree of semi-hardening, the colloid fraction of the semi-hardened film or sheet is usually in the range of 20 to 90%, preferably 30 to 85%, more preferably 40 to 80%. When the colloid fraction of the semi-hardened film or sheet is within the above range, the shape of the film or sheet can be maintained, and even if the shape is deformed by secondary hardening, good thickness precision can be obtained. When the allyl ester resin composition contains a photopolymerization initiator, the colloid fraction can be adjusted by changing the amount of irradiation of an active energy ray such as ultraviolet rays. When the allyl ester resin composition contains only the thermal polymerization initiator, the heating temperature and the heating time can be appropriately adjusted to form a desired colloid fraction (semi-hardened state).

The colloid fraction is expressed by the mass fraction of the component remaining as an insoluble component when the resin composition is dissolved in a solvent.

[Math 1] Colloid fraction (%) = 100 × {(insoluble component mass) / (original resin composition mass)}

As the solvent, a solvent capable of dissolving each component of the resin composition (excluding inorganic substances) can be used. Specifically, acetone, toluene, xylene, etc. are preferred. Solvent. The insoluble matter can be determined by a Soxhlet extraction method or a filtration method, a metal mesh bag, a tea bag method, or the like.

The substrate is not particularly limited as long as it does not cause rapid deterioration even when the active energy ray is irradiated. For example, a film or sheet of polyethylene, polypropylene, polyethylene terephthalate, metal or glass can be used. When the cover film or sheet is used, it is preferably made of the same material, shape and size as the substrate. This is to reduce the difference in shrinkage or strain between the substrate and the cover film or sheet. When irradiating the active energy ray, the cover film or sheet must use a material that allows the activation energy to penetrate.

The substrate and the cover film or sheet are preferably provided with a release layer formed by applying a release agent, and are provided as a release sheet, and are provided on the semi-hardened film, for the purpose of easily peeling off the semi-cured film or sheet from the substrate. Or one or both sides of the sheet. The release sheet is stretched (coated) on the release sheet so as to have a predetermined thickness after curing, and is irradiated with energy rays from the side of the resin composition after coating to form a resin composition. The semi-hardened film or sheet is then laminated and peeled off, whereby a semi-hardened film or sheet provided with a release sheet on both sides can be obtained.

As the release agent, a release agent containing an alkyd resin or a polyoxymethylene resin can be used. The release layer is provided by applying a release agent to the surface of the substrate. The method of stretching the allyl ester resin composition on the substrate is not particularly limited, and for example, it can be carried out by various coating methods such as roll coating, spraying, and spin coating. The coating amount of the resin composition may be appropriately selected so that the thickness of the resin composition after hardening becomes a desired thickness to be described later.

Examples of the active energy ray include ionizing radiation, that is, ultraviolet rays or electron beams. When using ultraviolet rays as ionizing radiation, it is only necessary to use light containing ultraviolet rays having a wavelength of 190 to 380 nm. The amount of ultraviolet rays can be appropriately selected depending on the thickness of the allyl ester resin composition or film sheet to be used, and is usually about 10 to 1000 mJ/cm ² , preferably 10 to 700 mJ/cm ² , more preferably 100 to 500 mJ. /cm ² . The ultraviolet source is not particularly limited, and for example, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a carbon arc lamp, or the like can be used.

When an electron beam is used as the ionizing radiation, the acceleration voltage can be appropriately selected depending on the thickness of the resin composition or film sheet to be used. Usually, the acceleration voltage is preferably about 70 to 300 kV. Further, the amount of the irradiation line is preferably an amount such that the resin composition is colloidal, and is usually selected from the range of 5 to 300 gGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad). The electron beam source is not particularly limited, and for example, a Kockrov-Walton type, a Vandergrave type, a resonant transformer type, an insulated core transformer type, or a linear type, a high frequency high voltage type, a high frequency type, etc. can be used. Various electron beam accelerators.

Further, the semi-hardening can also be carried out by heating. At this time, it is preferred to contain a thermal polymerization initiator as a hardener. According to the semi-hardening by heating, the decomposition temperature of the thermal polymerization initiator can be considered, and it is carried out at a relatively low temperature and in a short time. When the temperature is too high, the temperature rises due to the heat of reaction, so that the reaction cannot be stopped in the semi-hardened state, and there is a fear that the reaction proceeds to a state in which plastic deformation is impossible. When semi-hardening is performed only by heating, a thermal polymerization initiator having a different decomposition temperature may be used in combination.

The thickness of the semi-hardened film sheet obtained as described above can be appropriately selected depending on the application, and is usually 0.05 to 3.0 mm, preferably 0.1 to 1.0 mm.

[Formed product and its manufacturing method]

Next, the molded article of the present invention will be described. The molded article can be obtained by molding a film or sheet of a semi-cured allyl ester resin composition into a desired three-dimensional shape using a mold or the like, and performing secondary hardening while maintaining the shape. Secondary hardening is preferably carried out by heating. The secondary hardening is performed until the hardening reaction is almost completed. The standard is a gel fraction of 90% or more. In this state, even if it is separated from the mold, it is not plastically deformed, and the shape can be maintained.

The heating temperature of the secondary hardening varies depending on the type of the radical polymerization initiator to be used, and is usually from 100 ° C to 200 ° C, preferably from 120 to 180 ° C. When it is 100 ° C or less, hardening does not proceed sufficiently, and when it exceeds 200 ° C, it is easy to color.

A method of forming a film or sheet of a semi-cured allyl ester resin composition into a desired three-dimensional shape and heating it to perform secondary hardening, and examples thereof include compression molding, vacuum molding, free-blowing molding, pressure forming, and die-cutting. Forming method, etc. The shape of the secondary hardened product is determined by the molding conditions and the shape of the mold. In addition to a simple shape such as a rectangular parallelepiped, a cylinder, a square column, a rod shape, a hemisphere shape, a quadric surface, a cubic surface, or the like, it may be formed as shown in Fig. 1 (a) (two sheets of a sheet-like sheet having the same width) The side end portion is bent into a vertical shape), (b) (a sheet having a curved surface), (c) a shape used for a cover such as a tablet PC, and (d) (the lid of the petri dish or the container) Shape) Miscellaneous shape. The desired shape can be maintained in the mold until almost completely hardened, and from the viewpoint of dimensional accuracy of the formed shape, compression molding is preferred.

After the secondary hardening, the molded article can be further heated (post-hardened) in order to completely harden. The temperature at this time is preferably set to be higher than the temperature of secondary hardening.

Further, when the final molded article is a quadric surface such as a cylinder, other film or sheet material may be laminated to the semi-cured allyl ester resin composition by secondary processing.

Examples of other film sheet materials constituting the molded article include polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polymethyl methacrylate, and cycloolefin polymer (for example, Japan Zeon Co., Ltd. ZEONEX (registered trademark) manufactured by the company, cellulose triacetate, polyimine (for example, Neoprim (registered trademark) L manufactured by Mitsubishi Gas Chemical Co., Ltd.), and polyarylamine (for example, Mictron manufactured by Toray Co., Ltd. (registered) Trademark)), polyether oxime (for example, Sumika Eccel (registered trademark) PES manufactured by Sumitomo Chemical Co., Ltd.), siloxane-based polymer (for example, Sil Plus (registered trademark) manufactured by Nippon Steel Chemical Co., Ltd.), fluorine system Polymer (for example, Dyneon (registered trademark) PTFE manufactured by Sumitomo 3M Co., Ltd.), amorphous polyolefin (for example, Apel (registered trademark) manufactured by Mitsui Chemicals, Inc.), unsaturated polyester resin, vinyl ester resin, epoxy Resin and urethane acrylate resin. Transparent materials are sometimes used depending on the use of the molded product.

In order to impart functionality to the molded article of the present invention, a hard coat layer, a gas barrier coating layer, an antireflection film layer, and a conductive film layer may be laminated.

In the semi-hardened allyl ester resin composition film sheet and other film layers In combination, the adhesive layer may not be interposed, but may be directly bonded by heat treatment of secondary processing.

The molded article of the three-dimensional shape of the present invention is suitable as an optical material, and is applicable to display device members or illumination members of liquid crystals, organic EL displays, touch panels, etc., and is particularly applicable to portable windows and tablet PC windows. A cover for a touch panel, a touch panel substrate, a transparent printed substrate, 3D glasses, and the like.

[Examples]

Hereinafter, the present invention will be specifically described by way of Synthesis Examples and Examples, but the present invention is not limited thereto.

[Colloid fraction]

The colloidal fraction of the semi-hardened or cured film described in the examples was measured by the following method.

The semi-hardened or hardened film was refluxed in acetone for 4 hours, and after extracting the soluble component, the solid component was filtered. The obtained solid component was dried at 100 ° C for 2 hours, and the colloid fraction was calculated by the following calculation formula.

[Math 2] Colloid fraction (%) = (W ₁ /W ₀ ) × 100

Where W ₀ is the mass of the film before extraction and W ₁ is the mass of the solid component after extraction and drying

Synthesis Example 1: Synthesis of allyl ester oligomer (1)

1625 g of diallyl terephthalate, 167 g of propylene glycol, and 0.813 g of dibutyltin oxide were placed in a 2-liter three-necked flask equipped with a distillation apparatus, and the reaction was carried out at 180 ° C in a nitrogen gas stream. Heating is continued while distilling off the allyl alcohol produced by the transesterification reaction. When the distilled allyl alcohol was about 170 g, the pressure in the reaction system was gradually reduced to 6.6 kPa in about 4 hours to accelerate the distillation rate of allyl alcohol. When the distillate was hardly produced, the pressure in the reaction system was reduced to 0.5 kPa, and after further reacting for 1 hour, the reaction product was cooled. Hereinafter, the reaction product obtained by this is referred to as "allyl ester oligomer (1)".

Synthesis Example 2: Synthesis of allyl ester oligomer (2)

1625 g of diallyl 1,4-cyclohexanedicarboxylate, 167 g of trimethylolpropane, and 0.813 g of dibutyltin oxide were placed in a 2-liter three-necked flask equipped with a distillation apparatus, and the same manner as in Synthesis Example 1. reaction. Hereinafter, the reaction product obtained by the reaction is referred to as "allyl ester oligomer (2)".

Example 1

70 parts by mass of allyl ester oligomer (1) produced in Synthesis Example 1 and 30 parts by mass of trimethylolpropane triacrylate, and 1 part by mass of PERHEXA (registered trademark) HC (manufactured by Nippon Oil Co., Ltd.) 0.5 parts by mass of IRGACURE (registered trademark) 184 (manufactured by BASF Corporation) was mixed until uniformity was obtained, and the allyl ester resin composition (1) was prepared. Next, the resin composition was applied to a PET film having a thickness of 100 μm using a wet film coater so that the thickness after hardening became 200 μm. After the PET film having a thickness of 100 μm was coated on the coated surface, ultraviolet rays were irradiated under conditions of 200 mW/cm ² and 800 mJ/cm ² using an ultraviolet irradiation device (Eyegrandage, metal halide lamp manufactured by Eyegraphics Co., Ltd.) to form a resin composition. A semi-hardened film is obtained by colloidalization (semi-hardening). The semi-hardened film has a colloid fraction of 76%.

After the obtained semi-hardened film is processed into a size of 3 cm × 7 cm, peeling The single-sided PET film was wound so as to be in contact with a rod made of SUS (diameter: 3 cm, manufactured by SUS304), and fixed with a polyimide tape. This was placed in a forced convection oven maintained at 160 ° C, and after secondary hardening for 1 hour, it was peeled off from a rod made of SUS to obtain a cured product. Subsequently, annealing was performed at 180 ° C for 1 hour to obtain a transparent cured product which was formed into a three-dimensional shape (cylindrical shape) as shown in the photograph of Fig. 3 . The cured product had a colloid fraction of 99%.

Example 2

80 parts by mass of the allyl ester oligomer (2) produced in Synthesis Example 2 and 20 parts by mass of trimethylolpropane triacrylate, and 1 part by mass of PERHEXYL (registered trademark) I (manufactured by Nippon Oil Co., Ltd.) 0.5 parts by mass of DAROCURE (registered trademark) TPO (manufactured by BASF Corporation) was mixed until uniformity was obtained, and the allyl ester resin composition (2) was prepared. Next, the resin composition was applied to a PET film having a thickness of 100 μm using a wet film coater so that the thickness after hardening became 200 μm. After the PET film having a thickness of 100 μm was coated on the coated surface, ultraviolet rays were irradiated under conditions of 200 mW/cm ² and 50 mJ/cm ² using an ultraviolet irradiation device (Eyegrandage, metal halide lamp manufactured by Eyegraphics Co., Ltd.) to form a resin composition. A semi-hardened film is obtained by colloidalization (semi-hardening). The semi-hardened film has a colloid fraction of 48%.

After the obtained semi-hardened film was processed into a size of 2 cm × 4 cm, the single-sided PET film was peeled off, and the surface was wound in contact with a rod made of SUS (diameter: 3 cm, manufactured by SUS304), and polyimine was used. The tape is fixed. This was placed in a forced convection oven maintained at 160 ° C for 1 hour. After the secondary hardening, it was peeled off from the rod made of SUS to obtain a cured product. Subsequently, annealing was performed at 180 ° C for 1 hour to obtain a transparent cured product which was formed into a three-dimensional shape (circular arc shape) as shown in the photograph of Fig. 4 . The cured product had a colloid fraction of 99%.

Example 3

The ultraviolet irradiation time of Example 2 was adjusted to irradiate ultraviolet rays of 200 mJ/cm ² to obtain a semi-hardened film. The semi-hardened film had a colloid fraction of 67%.

The obtained semi-cured film was treated in the same manner as in Example 2 to obtain a transparent cured product which was formed into a three-dimensional shape (circular arc shape) as shown in the photograph of Fig. 5. The cured product had a colloid fraction of 99%.

Example 4

The allyl ester resin composition (2) was applied to a PET film having a thickness of 100 μm using a wet film coater so that the thickness after hardening became 500 μm. Then, a PET film having a thickness of 100 μm was coated on the coated surface, and then irradiated with ultraviolet rays under conditions of 300 mW/cm ² and 800 mJ/cm ² using the ultraviolet irradiation device to form a semi-hardened film by colloidalizing (semi-hardening) the resin composition. . The semi-hardened film has a colloidal fraction of 79%.

The obtained semi-hardened film was processed into a size of 10 cm × 5.5 cm, and was exposed to a curved plate made of SUS (a diameter of 50 cm, a length of 30 cm, a width of 30 cm, a thickness of SUS304, and a thickness) in a state in which a double-sided PET film was attached. 2mm) way, fixed with polyimide tape. Load this into hold The forced convection oven at 160 ° C was subjected to secondary hardening for 1 hour, and then peeled off from a curved plate made of SUS to obtain a cured product. Subsequently, after peeling off the double-sided PET film, annealing was performed at 180 ° C for 10 minutes to obtain a transparent cured product which was formed into a three-dimensional shape as shown in the photograph of Fig. 6 . The cured product had a colloid fraction of 99%.

Example 5

The semi-hardened film obtained in the same manner as in Example 4 was processed into a size of 10 cm × 5.5 cm, and then wound in a glass-made cylinder (diameter 10.5 cm, length) in a state in which a double-sided PET film was attached. 30 cm, Pyrex (registered trademark) heat-resistant glass, thickness 1.5 mm), fixed with a polyimide tape. This was placed in a forced convection oven maintained at 160 ° C, and after secondary hardening for 1 hour, it was peeled off from a glass cylinder to obtain a cured product. Subsequently, after peeling off the double-sided PET film, annealing was performed at 180 ° C for 10 minutes to obtain a transparent cured product which was formed into a three-dimensional shape as shown in the photograph of Fig. 7 . The cured product had a colloid fraction of 99%.

Comparative example 1

The allyl ester resin composition (2) of Example 2 was applied to a PET film having a thickness of 100 μm using a wet film coater so that the thickness after hardening became 200 μm. After the PET film having a thickness of 100 μm was coated on the coated surface, the film was processed to a size of 2 cm × 4 cm without being irradiated with ultraviolet rays, and then the PET film of one side was peeled off so that the surface was in contact with a rod made of SUS (diameter It was wound in a manner of 3 cm and made of SUS304 and fixed with a polyimide tape. At this time, the allyl ester resin composition (2) has a colloid fraction of 0% and a viscosity of about 1200 mPa. s, and flows when wound around the SUS rod, and the cylindrical shape cannot be maintained. This was placed in a forced convection oven maintained at 160 ° C, and after hardening for 1 hour, it was peeled off from a rod made of SUS to obtain a cured product. Subsequently, annealing was performed at 180 ° C for 1 hour to obtain a molded body. However, the thickness was not uniform, and it was observed that the film was oozing out from the PET film, and the shape could not be a predetermined shape. The cured product had a colloid fraction of 99%.

Comparative example 2

The ultraviolet irradiation time of Example 2 was adjusted to irradiate ultraviolet rays of 2000 mJ/cm ² , and then heated at 160 ° C for 10 minutes to obtain a substantially hardened film. The hardened film had a colloidal fraction of 95%. After the obtained cured film was processed to a size of 2 cm × 4 cm, the PET film of one side was peeled off, and the surface was wound in contact with a rod made of SUS (diameter: 3 cm, manufactured by SUS304), but cracked and could not be carried out. In the secondary hardening step, a cylindrical molded body could not be obtained.

The results of Examples 1 to 5 and Comparative Examples 1 and 2 are collectively shown in the first table.

Claims (6)

A method for producing a cured resin molded article, which is characterized in that semi-hardening is carried out by heating or activating an energy ray so that the colloid fraction of the film or sheet of the allyl ester resin composition is 40 to 80%. The latter film or sheet is formed into a desired three-dimensional shape, and is subjected to secondary hardening by heating while maintaining the aforementioned shape. A method for producing a cured resin molded article, characterized in that the film is semi-hardened by heating or activating the energy ray so that the colloid fraction of the film or sheet of the allyl ester resin composition is 40 to 80%. After the film is bonded to the semi-cured film or sheet, it is formed into a desired three-dimensional shape, and is subjected to secondary hardening by heating while maintaining the shape described above. The method for producing a cured resin molded article according to the first or second aspect of the invention, wherein the allyl ester resin composition contains a photopolymerization initiator and a thermal polymerization initiator, and the above-mentioned alkene is carried out by light irradiation. The semi-hardening of the propyl ester resin composition is subjected to secondary hardening by heating. The method for producing a cured resin molded article according to claim 2, wherein the other film or sheet is selected from the group consisting of allyl ester resin, polyethylene terephthalate, polyethylene naphthalate, and polycarbonate. Ester, polymethyl methacrylate, cycloolefin polymer, cellulose triacetate, polyimine, polyarylamine, polyether oxime, siloxane polymer, fluoropolymer, amorphous poly A film or sheet of a resin of an olefin, an unsaturated polyester resin, a vinyl ester resin, an epoxy resin, and an urethane acrylate resin. For example, the manufacturer of the cured resin molded article of claim 3 A method in which secondary hardening is performed by heating in a mold. The method for producing a cured resin molded article according to claim 1 or 2, wherein the allyl ester resin composition contains an allyl ester oligomer having a general formula (2) The base is used as a terminal group, and has a structure represented by the general formula (3) as a constituent unit; (wherein R ³ represents a hydrogen atom or a methyl group, and A ² represents one or more organic residues having an alicyclic structure and/or an aromatic ring structure derived from a dicarboxylic acid); (wherein A ³ represents one or more organic residues having an alicyclic structure and/or an aromatic ring structure derived from a dicarboxylic acid, and X represents one or more organic residues derived from a polyhydric alcohol; From the ester bond, a branching structure having a group represented by the above general formula (2) as a terminal group and a structure represented by the above general formula (3) as a constituent unit is formed.