KR20130085419A - Process for production of cured film, and cured film - Google Patents

Abstract

This invention apply | coats curable resin composition (A) and the curable resin composition (B) on the surface of a 1st base material, respectively, and forms a curable resin layer, irradiates an energy beam, and cured film (I) and a cured film The third process of obtaining the 1st and 2nd laminated body which formed (II), and the cured film (II) of the said 1st laminated body, and the cured film (II) of a 2nd laminated body from curable resin composition (C). The step of obtaining a 3rd laminated body by irradiating an energy ray after bonding through a curable resin layer, and hardening a 3rd curable resin layer, and peeling a 1st base material and a 2nd base material from the said 3rd laminated body, and said cured film (I ) And a method for producing a cured film including a step of obtaining a laminated cured film (III) of a cured film (II). According to this invention, the cured film which is excellent in transparency which has a fixed thickness, and heat resistance, and is high in thickness precision can be obtained.

Description

Production method and cured film of a cured film {PROCESS FOR PRODUCTION OF CURED FILM, AND CURED FILM}

The present invention relates to a method for producing a cured film. Moreover, it is related with the manufacturing method of the transparent cured film suitable for the use of a display substrate, a solar cell substrate, etc. which have a certain thickness, and the cured film manufactured by the method in detail.

Conventionally, glass has been used as a display substrate or a solar cell substrate such as a liquid crystal display, an organic EL display, a touch panel, and the like, but a replacement to a plastic substrate is being considered due to its characteristics such as light weight and brittleness. Plastic films of thickness and methods of making the same have been proposed.

The film using curable resin composition can be manufactured by apply | coating curable resin composition on a lower support base material, laminating | stacking an upper support base material on it, and then irradiating and hardening an energy beam, such as an ultraviolet-ray, and peeling both support base materials. (For example, patent document 1: Unexamined-Japanese-Patent No. 2002-012682). However, when making a cured film by this method, the coating thickness of curable resin composition is about 0.1-0.5 mm, and when apply | coating at thickness more than this, it becomes easy to produce the deformation defect of cured film by hardening shrinkage of resin, and also the thickness precision In view of deterioration, it is difficult to stably obtain a film having a certain thickness.

In addition, Patent Document 2 (Japanese Patent Laid-Open No. 2007-290364) discloses a method for producing a cured film in which a supporting substrate is prepared in advance by the above method, and then the same curable resin layer is formed between the substrates and cured using the supporting substrate. Although proposed, the support base material formed with the same composition as curable resin peels after hardening by performing energy-beam irradiation to curable resin layer, and is not a method of providing an integrated film. Patent Document 3 (International Publication No. 2009/128415 Pamphlet (US2011039117 Al)) is a coating agent for applying a curable resin composition to the surfaces of the first and second substrates for the purpose of suppressing deformation such as warping during heating / cooling. 1st process, the 2nd process of bonding together and bonding curable resin composition layers formed in each surface of the said 1st and 2nd base material, and the 3rd process of hardening curable resin composition layer between the said 1st and 2nd base material The manufacturing method of the curable film characterized by having is disclosed. This method bonds curable resin composition layers between a 1st and 2nd base material in an uncured state, and bonds them, and does not laminate | stack the film which the curable resin composition layer hardened | cured.

Japanese Patent Publication No. 2002-012682 Japanese Patent Publication No. 2007-290364 International Publication No. 2009/128415 Pamphlet

An object of this invention is to provide the manufacturing method of the cured film which is excellent in transparency which has a fixed thickness, heat resistance, and high thickness precision using curable resin composition.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining the said subject, the present inventors discovered that the film which is excellent in transparency and heat resistance which has a certain thickness, and high thickness precision was obtained by the specific manufacturing method, and came to complete this invention. That is, this invention relates to the manufacturing method of the following films, and the cured film obtained by the manufacturing method.

[1] A first laminate comprising a curable resin composition (A) applied to the surface of a first base material to form a first curable resin layer, and irradiating an energy ray to the first curable resin layer to form a cured film (I). Curable resin composition (B) was apply | coated to the 1st process of obtaining the surface of a 2nd base material, and a 2nd curable resin layer was formed, energy beam was irradiated to the said 2nd curable resin layer, and the cured film (II) was formed. 2nd process of obtaining a 2nd laminated body, and the 3rd curable resin layer which consists of curable resin composition (C) and the cured film (I) of the said 1st laminated body, and the cured film (II) of a said 2nd laminated body. And bonding to the first substrate and the second substrate from the third step of obtaining a third laminate by irradiating an energy ray and curing the third curable resin layer, and the third laminate, and the cured film (I ) And the agent for obtaining a laminated cured film (III) of the cured film (II) The manufacturing method of the cured film containing 4 process.

[2] The method of [1], wherein the first and / or the second curable resin layer of the first and / or the second curable resin layer is irradiated with an energy ray before the first and / or the second curable resin layer is irradiated. The method further includes a step of attaching the cover film to the surface, and further comprising the step of peeling the cover film before applying the curable resin composition (C) in the third step.

[3] The bonding according to [1] or [2], wherein the bonding through the third curable resin layer of the cured film (I) and the cured film (II) in the third step is performed on the cured film (I). In the process of apply | coating curable resin composition (C), forming a 3rd curable resin layer, adhering the said cured film (II) to the said 3rd curable resin layer, and irradiating an energy ray to harden a 3rd curable resin layer. The manufacturing method of the cured film characterized by the above-mentioned.

[4] The method for producing a cured film according to any one of [1] to [3], further comprising the step of performing heat treatment after irradiation with the energy ray in the third step.

[5] The method for producing a cured film according to any one of [1] to [4], further comprising a step of cutting the third laminate to a desired dimension by a laser before the fourth step.

[6] The method for producing a cured film according to any one of [1] to [5], wherein the cured film (I) and the cured film (II) are semi-hardened films.

[7] The method for producing a cured film according to any one of [1] to [6], wherein the cured film (I) and the cured film (II) have the same film thickness produced under the same composition and conditions.

[8] The method for producing a cured film according to any one of [1] to [7], wherein the thickness of the laminated cured film (III) is 0.5 to 1.5 mm.

[9] The method for producing a cured film according to any one of [1] to [8], wherein the composition of the curable resin composition (A), the curable resin composition (B), and the curable resin composition (C) is the same. .

[10] The curable resin composition (A), the curable resin composition (B), or the curable resin composition (C) according to any one of [1] to [9], wherein allyl ester resins and photoinitiators are included. The manufacturing method of the cured film to make.

[11] The method for producing a cured film according to [10], wherein the curable resin composition (A), the curable resin composition (B), and the curable resin composition (C) further include a thermal initiator.

[12] The viscosity at 25 ° C of the curable resin composition (A), the curable resin composition (B), and the curable resin composition (C) according to any one of [1] to [11], respectively, is 100 to 10000 mPa · s. It is a manufacturing method of the cured film characterized by the above-mentioned.

[13] A cured film produced by the production method of any one of [1] to [12].

(Effects of the Invention)

ADVANTAGE OF THE INVENTION According to this invention, the film which is excellent in transparency and heat resistance which have a certain thickness suitable for uses, such as a display board | substrate, a solar cell board | substrate, and high thickness precision at low birefringence can be obtained.

Hereinafter, the present invention will be described in detail.

The manufacturing method of the cured film of this invention apply | coats curable resin composition (A) to the surface of a 1st base material, forms a 1st curable resin layer, irradiates an energy ray to the said 1st curable resin layer, and applies cured film (I). Applying curable resin composition (B) to the 1st process of obtaining the formed 1st laminated body and the surface of a 2nd base material, and forming a 2nd curable resin layer, irradiating an energy ray to the said 2nd curable resin layer, and a cured film 2nd process of obtaining the 2nd laminated body which formed (II), and the cured film (II) of the said 1st laminated body, and the cured film (II) of the said 2nd laminated body which consists of curable resin composition (C) 3rd process of obtaining a 3rd laminated body by irradiating an energy ray and hardening | curing a 3rd curable resin layer after bonding through 3 curable resin layer, and peeling a 1st base material and a 2nd base material from the said 3rd laminated body, Cured film (I) and cured film (II) In that it comprises a fourth step for obtaining a laminated cured film (Ⅲ) features. That is, with the process of manufacturing a cured film using a support base material (corresponding to the said 1st process and a 2nd process), the process of joining and unifying two cured films (corresponding to said 3rd process), and the obtained laminated body From the support substrate (corresponding to the fourth step). As used herein, the term "film" is not limited to a thin film having a thickness of less than 0.25 mm as defined in a so-called JIS packaging term standard (JIS Z0108), and includes a thin sheet (sheet) having a thickness of 0.25 mm or more. .

[1st process and 2nd process]

These processes are processes of manufacturing two laminated bodies (the said 1st laminated body and the 2nd laminated body) provided with the cured film, respectively, on the support base material (the said 1st base material and the 2nd base material), and a 1st base material and the 1st base material After apply | coating curable resin composition (A) and curable resin composition (B) on 2 base materials, energy beam is irradiated and cured film (I) and cured film (II) are manufactured.

The 1st and 2nd curable resin layer formed on the support base material is hardened by irradiating an energy beam. At this time, in order to perform energy ray irradiation via a support base material, what transmits an energy ray as a support base material is used. As the supporting base material, for example, films such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), cycloolefin polymer (COP), cycloolefin copolymer (COC) can be used. It is not limited to. PET film is preferable from transparency and the availability. Moreover, as for these support base materials, it is more preferable that the application surface was peeled off. As the peeling treatment, for example, a mold release agent having a curable silicone resin as a main component, a mold release agent of a modified silicone type by graft polymerization with organic resins such as a urethane resin, an epoxy resin, an alkyd resin, or a fluorine resin as a main component And a treatment for coating a release agent such as corona treatment or the like.

The method for applying the curable resin composition (A) and the curable resin composition (B) to the supporting substrate is not particularly limited as long as it is an application method having excellent uniformity and application shape, and is a die coating method, a doctor coating method, a knife coating method, a bar coating method. Known coating methods, such as a method, can be used. Coating thickness is about 10-500 micrometers normally, Preferably it is 20-400 micrometers, More preferably, it is 50-300 micrometers. If the coating thickness is less than the lower limit, the coating tends to be difficult to apply uniformly, and if the coating thickness exceeds the upper limit, the cured shrinkage tends to cause deformation defects of the cured film, and the thickness accuracy also tends to deteriorate.

As an energy ray used for hardening of the 1st and 2nd curable resin layer obtained by apply | coating curable resin composition (A) and curable resin composition (B), rays, such as an ultraviolet-ray, an ultraviolet-ray, a near-ultraviolet, infrared, X-rays, (gamma), Although electromagnetic waves, such as a line | wire, an electron beam, a neutron beam, etc. can be used, an ultraviolet-ray is preferable from a hardening rate, the availability of an irradiation apparatus, a price, etc. In addition, although irradiation may be sufficient from one side and may be simultaneous from both surfaces, simultaneous irradiation from both surfaces is more preferable from a uniformity of hardening, and an efficiency.

When using ultraviolet rays, a light source including ultraviolet rays having a wavelength of 190 to 380 nm, for example, a high pressure mercury lamp, a low pressure mercury lamp, and a metal halide lamp is used. As the amount of ultraviolet rays, the dose at which the curable resin layer is in a semi-cured state is preferable, usually about 50 to 1000 mJ / cm 2, preferably 100 to 800 mJ / cm 2, and more preferably 150 to 500 mJ / cm 2.

In the present specification, the term "semicuring" is gelated by irradiating an energy ray to the curable resin layer, but means a state where the gel fraction is less than 100% without completely terminating the reaction, and the monomer or oligomer contained in the curable resin composition. Although a three-dimensional network structure is formed by a part of crosslinking reaction, it is the state in which the unreacted reaction component is maintained in the said network structure.

As the degree of gelation, the gel fraction is in the range of 5 to 80%, preferably 10 to 70%, more preferably 20 to 60%. When the gel fraction of the semi-cured film is in the above range, the film shape can be maintained, so that a good thickness precision can be obtained, and furthermore, in the laminated surface after laminating curable resin between semi-curable films described later and performing energy ray curing and thermal curing, Peeling can be prevented. A gel fraction is an index which shows the degree of hardening of a semi-hardened film here, and is represented by the ratio with respect to the mass before extraction of the mass of the dry film after 3 hours of extraction by acetone reflux.

It is preferable to perform energy ray irradiation in nitrogen atmosphere or the state which a cover film adhered in order to prevent hardening inhibition by oxygen. There is no restriction | limiting in particular as a cover film as long as it permeate | transmits an energy ray, Films, such as PET, PEN, PC, COP, COC, can be used, It may be the same as a support base material, and may be different. Especially, PET film is preferable from transparency and the ease of acquisition, and it is more preferable that the peeling process is given to the peeling surface similarly to the case of a support base material. Although it is preferable to use ultraviolet (UV) as an energy ray, it is also possible to use an electron beam (EB).

The composition of curable resin composition (A) and curable resin composition (B) used at a 1st process and a 2nd process may be the same, and may differ. Moreover, these hardening conditions may also be the same and may differ. However, when other compositions and conditions are used, it is preferable to use ones manufactured under the same composition and conditions because the behavior during complete curing is different, which tends to cause warpage and distortion. When the high uniformity of the film is required, it is preferable to use the same composition. When using a different composition, the film which does not impair an optical characteristic can be obtained by giving consideration, such as adjusting refractive index. Moreover, even if it is the same composition, since there exists a tendency for bending, a distortion, etc. to occur similarly in thickness, it is more preferable to use the thing of the same thickness. The composition of curable resin composition is mentioned later.

[Third Step]

This process is a process of laminating | stacking the cured film (I) and cured film (II) of the 1st laminated body and 2nd laminated body obtained at the said 1st process and the 2nd process, and curable resin composition between the cured films on a base material. After bonding through the 3rd curable resin layer which consists of (C), a 3rd laminated body is obtained by irradiating an energy ray and hardening a 3rd curable resin layer. In addition, when a cover film is affixed on the surface of a 1st and / or 2nd curable resin layer before irradiating an energy ray to a 1st and / or 2nd curable resin layer in a said 1st process and a 2nd process, a cover After peeling a film, a 3rd process is implemented.

The method of interposing a 3rd curable resin layer between cured film (I) and cured film (II) is not specifically limited. For example, after (1) apply | coating a 3rd curable resin layer to the surface of one cured film, and attaching the other cured film to a 3rd curable resin layer, (2) 3rd each to the surface of both cured films After apply | coating curable resin layer, the method of sticking together 3rd curable resin layer, (3) The method of hardening | curing while interposing the semi-hardened film which semi-hardened the 3rd curable resin layer between both cured films, and laminating | stacking and crimping | bonding. Although etc. are mentioned, It is preferable to use the method of (1) whose manufacturing process is simple.

Although it is preferable that the application | coating method of curable resin composition (C) is the same as the application | coating method in the said 1st process and a 2nd process, if it is an application | coating system excellent in uniformity and application shape, it will not specifically limit. The energy ray irradiation step is also preferably the same as the irradiation method in the first step and the second step, but is not particularly limited as long as the third curable resin layer is obtained in a desired curing state. The third curable resin layer is cured by irradiating with energy ray through at least one of the first laminate and the second laminate.

When energy ray irradiation to a 3rd curable resin layer is insufficient, ie, the hardening of a 3rd curable resin layer is insufficient, hardening can be fully advanced by heat hardening. In order to fully advance hardening by heat-hardening, it is preferable to mix | blend a thermal initiator in curable resin beforehand. Moreover, it is preferable that the thermal initiator used at this time has a half-life of 1 minute in a heating temperature range (half-life becomes 1 minute in a heating temperature range). Although heating temperature is not specifically limited, It is the range of 100-200 degreeC, Preferably it is 120-190 degreeC, More preferably, it is 140-180 degreeC. If the heating temperature is less than the above range, the thermal initiator may be consumed by the curing heat generation in the energy ray irradiation step. If the above heating range is exceeded, the heat resistance of the supporting substrate becomes insufficient, and the kink (wrinkle or irregularities) Occurring phenomenon) and the like are not preferable because they tend to occur.

The heating device used for heat curing is not particularly limited, but hot air drying furnace, infrared heating furnace and the like can be used, but the surface and inside of the film can be heated uniformly, and the occurrence of distortion due to uneven heating can be avoided. Infrared heating furnace is preferred.

The composition of the curable resin composition (C) used in the third step may be the same as or different from the composition of the curable resin composition (A) and the curable resin composition (B) used in the first step and the second step. Moreover, hardening conditions may be the same and may differ. However, when the high uniformity of the film is required, it is preferable to use the same composition. When using other curable resin, the film which does not impair an optical characteristic can be obtained by consideration, such as adjusting refractive index. In addition, since the 3rd curable resin layer which consists of curable resin composition (C) is hardened | cured by irradiating an energy ray through at least one of a 1st laminated body and a 2nd laminated body, when it does not use heat hardening together, the said 1st and It is preferable to carry out on conditions stronger than the energy-beam irradiation conditions in hardening of a 2nd curable resin layer.

[Fourth Step]

This process is a process of peeling a support base material from the 3rd laminated body obtained by the said 3rd process, The 1st and 2nd support base materials used at the said 1st process and a 2nd process are peeled simultaneously or one side, and a laminated cured film ( III) is produced. The support base material can be peeled off after the third laminate is cut into desired dimensions in advance. In addition, although it can also cut | disconnect to a desired dimension after peeling, in this case, a distortion or thickness nonuniformity at the time of application | coating may generate | occur | produce in this case, and peeling a base material from cutting the end surface beforehand, such as a crack from the end surface at the time of peeling, etc. It is preferable at the point which prevents generation. Although the cutting method to a desired dimension or the cutting method of an end surface are not specifically limited, The cutting by a laser is suitable.

By the said 1st-4th process, the laminated cured film (III) with a small thickness nonuniformity whose thickness is 0.5-1.5 mm can be obtained.

[Curable resin composition]

Curable resin composition (A), curable resin composition (B), and curable resin composition (C) used for this invention are not specifically limited as long as it hardens | cures by energy-beam irradiation, In order to obtain the film excellent in heat resistance and transparency, allyl Preference is given to using ester resins. Moreover, in order to perform hardening by energy ray irradiation promptly, it is preferable to use together a (meth) acrylate monomer and / or an acrylate oligomer.

As allyl ester resin, the following general formula (1)

[Wherein R ¹ represents an allyl group or a metalyl group, and A ¹ represents an organic residue derived from a divalent carboxylic acid or carboxylic anhydride having at least one structure of a saturated and unsaturated hydrocarbon structure)

It has at least 1 sort (s) or more of group represented by the following as a terminal group, and also following General formula (2)

[Wherein A ² represents an organic residue derived from a divalent carboxylic acid or carboxylic anhydride having at least one of saturated and unsaturated hydrocarbon structures, and X represents one or more organic residues derived from a polyhydric alcohol. Indicates. However, X may further have a branched structure in which the general formula (1) is a terminal group by an ester bond and the general formula (2) is a repeating unit.

The allyl ester resin composition which has a group represented by a repeating unit is preferable.

R <^1> in the said General formula (1) represents an allyl group or a metalyl group. However, not all R <^1> in the terminal group represented by General formula (1) may be an allyl group or a metalyl group, and some may be nonpolymerizable groups, such as a methyl group or an ethyl group. In addition, A <^1> in General formula (1) is an organic residue derived from bivalent carboxylic acid. Although there is no restriction | limiting in particular as bivalent carboxylic acid, Aliphatic dicarboxylic acid, the aliphatic dicarboxylic acid containing an unsaturated group, and / or aromatic dicarboxylic acid, etc. are mentioned.

Specific examples of these divalent carboxylic acids include malonic acid, succinic acid, glutaric acid, adipic acid, 2-methylsuccinic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1 , 2-cyclohexanedicarboxylic acid, 4-methylcyclohexane-1,2-dicarboxylic acid, endomethylenetetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, methyltetrahydrophthalic acid, maleic acid, fumaric acid, ita Cholic acid, film laconic acid, terephthalic acid, isophthalic acid, orthophthalic acid, biphenyl-2,2'-dicarboxylic acid, biphenyl-3,3'-dicarboxylic acid, biphenyl-4,4'-dicar Acid, maleic methylcyclohexane tetrabasic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenyl-m, m'- Dicarboxylic acid, diphenyl-p, p'-dicarboxylic acid, benzophenone-4,4'-dicarboxylic acid, p-phenylenediacetic acid, p-carboxyphenylacetic acid, methylterephthalic acid, hete acid, te La bromine phthalic acid, and the like can be mentioned tetra-scroll acid, end acids and acid chloride Rend.

In general, aromatic dicarboxylic acids have high absorption of light, especially ultraviolet radiation, and in the case of UV curing, aliphatic dicarboxylic acids containing aliphatic dicarboxylic acids and / or unsaturated groups are preferred. Specific examples of the aliphatic dicarboxylic acid containing a divalent aliphatic dicarboxylic acid and / or an unsaturated group include malonic acid, succinic acid, glutaric acid, adipic acid, 2-methylsuccinic acid, 1,4-cyclohexanedicarboxylic acid , 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 4-methylcyclohexane-1,2-dicarboxylic acid, endomethylenetetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid And methyltetrahydrophthalic acid, maleic acid, fumaric acid, itaconic acid, film laconic acid, and the like.

In addition, in general formula (2), A <^2> is an organic residue derived from bivalent carboxylic acid or carboxylic anhydride. The divalent carboxylic acid or carboxylic anhydride is not particularly limited.

As such a divalent carboxylic acid or carboxylic anhydride, for example, malonic acid, succinic acid, glutaric acid, adipic acid, 2-methylsuccinic acid, 1,4-cyclohexanedicarboxylic acid, 1,3- Cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 4-methylcyclohexane-1,2-dicarboxylic acid, endomethylenetetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, methyltetrahydrophthalic acid , Maleic acid, fumaric acid, itaconic acid, film laconic acid, terephthalic acid, isophthalic acid, orthophthalic acid, biphenyl-2,2'-dicarboxylic acid, biphenyl-3,3'-dicarboxylic acid, biphenyl -4,4'-dicarboxylic acid, maleated methylcyclohexane tetrabasic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, Diphenyl-m, m'-dicarboxylic acid, diphenyl-p, p'-dicarboxylic acid, benzophenone-4,4'-dicarboxylic acid, p-phenylenediacetic acid, p-carboxyphenylacetic acid , There can be methyl terephthalic acid, Het acid, and tetra bromine phthalic acid, tetrahydro phthalic acid crawl, the end acid and the acid chloride Rend, it is not limited thereto.

In addition, X in the said General formula (2) represents the organic residue derived from the compound which has two or more hydroxyl groups. Specific examples of the compound having two or more hydroxyl groups include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, neopentylglycol, 1,6-hexanediol, 1,4- Cyclohexanedimethanol, diethylene glycol, ethylene oxide 3 mole adduct of isocyanuric acid, pentaerythritol tralyl ether, ditrimethylolpropane, tricyclodecane dimethanol, glycerin, trimethylolpropane, pentaerythritol ethylene jade Seed 3 mole adduct, D-sorbitol, hydrogenated bisphenol A, and the like. Although there is no restriction | limiting in particular as a manufacturing method of these polymeric compounds, For example, it can manufacture by the method enumerated in Unexamined-Japanese-Patent No. 6-74239.

There is no restriction | limiting in particular as a (meth) acrylate monomer and / or a (meth) acrylate oligomer which can be used together with an allyl ester resin in this invention, Various things can be used. In addition, a (meth) acrylate monomer and / or a (meth) acrylate oligomer means the monomer and / or oligomer which has a (meth) acryloyloxy group (methacryloyloxy group or acryloyloxy group).

Examples of the (meth) acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, and dodecyl (meth). Alkyl (meth) acrylates such as acrylate, octadecyl (meth) acrylate, cyclohexyl (meth) acrylate and methylcyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate , 1-naphthyl (meth) acrylate, fluorophenyl (meth) acrylate, chlorophenyl (meth) acrylate, cyanophenyl (meth) acrylate, methoxyphenyl (meth) acrylate and biphenyl (meth) Aryl (meth) acrylates such as acrylate,

Haloalkyl (meth) acrylates such as fluoromethyl (meth) acrylate and chloromethyl (meth) acrylate,

Also glycidyl (meth) acrylate, alkylamino (meth) acrylate and α-cyanoacrylic acid esters;

Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, 1 , 3-butylene glycol di (meth) acrylate, 1,4-butanedioldi (meth) acrylate, 1,5-pentadioldi (meth) acrylate, 1,6-hexadioldi (meth) acrylate , Neopentyl glycol di (meth) acrylate, oligoester di (meth) acrylate, polybutadienedi (meth) acrylate, 2,2-bis (4- (meth) acryloyloxyphenyl) propane and 2, Di (meth) acrylates such as 2-bis (4-ω- (meth) acryloyloxypolyethoxy) phenyl) propane, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, Pentaerythritol tetra (meth) acrylate, ethyl pentaerythritol Tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like of the ethylene oxide adducts; and trimethylolpropane tri (meth) acrylate is particularly preferred.

Examples of the (meth) acrylate oligomers include epoxy (meth) acrylates, urethane (meth) acrylates, polyester (meth) acrylates, polyether (meth) acrylates, acrylic (meth) acrylates, and unsaturated polyesters. Among these, epoxy (meth) acrylate is preferable.

Epoxy (meth) acrylate is also called vinyl ester resin, and generally ring-opening reaction of a carboxyl group of a compound having an epoxy group and a carboxyl compound having a polymerizable unsaturated group such as (meth) acrylic acid or a compound having a carboxyl group and glycidyl (meth) It is obtained by the ring-opening reaction of the epoxy group of the polymerizable unsaturated compound which has an epoxy group in molecules, such as) acrylate. In detail, it describes in the "polyester resin handbook" daily industrial newspaper, the 1988 publication, pages 336-357, etc., and can manufacture it by a well-known method.

As an epoxy-group containing compound used as a raw material of an epoxy (meth) acrylate, bisphenol A diglycidyl ether and its high molecular weight homologue, glycidyl ether of a bisphenol A alkylene oxide adduct, bisphenol F diglycidyl ether, and its high molecular weight Glycidyl ether of a homolog, a bisphenol F alkylene oxide adduct, a novolak-type polyglycidyl ether, etc. are mentioned.

Although hardening by curable resin composition of this invention by ultraviolet-ray (UV) irradiation is preferable, it is also possible to irradiate an electron beam (EB). Moreover, you may heat-harden as needed. When hardening, you may use a hardening | curing agent. There is no restriction | limiting in particular as a hardening | curing agent which can be used, What is generally used as a hardening | curing agent of polymeric resin can be used. Especially, the photoinitiator which is a radical polymerization initiator from the point of superposition | polymerization initiation by ultraviolet (UV) irradiation of the (meth) acryloyloxy group of the allyl group of a allyl ester resin, a (meth) acrylate monomer, and / or a (meth) acrylate oligomer, Preference is given to using. Moreover, when using heat hardening together, it is more preferable to use a thermal initiator.

There is no restriction | limiting in particular as a photoinitiator, Generally what is used as a photoinitiator of polymeric resin can be used. Specific examples thereof include 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexylphenyl ketone, benzophenone, 2-methyl-1- (4-methylthiophenyl) -2- Morpholinopropane-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2,4,6-trimethylbenzoyl diphenyl phosphine oxide etc. are mentioned.

These may be used individually by 1 type, and may be used in mixture or combination of 2 or more types.

Although there is no restriction | limiting in particular in the compounding quantity of these hardening | curing agents, It is preferable to mix | blend 0.1-10 mass parts with respect to 100 mass parts of curable resin compositions, and it is more preferable to mix | blend 0.5-5 mass parts. When the compounding quantity of a hardening | curing agent is less than 0.1 mass part, it is difficult to obtain sufficient hardening rate, and when a compounding quantity exceeds 10 mass parts, final hardened | cured material may fall back and mechanical strength may fall.

There is no restriction | limiting in particular as a thermal initiator used in this invention, Well-known organic peroxides, such as a dialkyl peroxide, an acyl peroxide, a hydroperoxide, a ketone peroxide, peroxy ester, can be used. Specific examples thereof include diisobutyryl peroxide, cumylperoxy neodecanoate, di-n-propylperoxydicarbonate, diisopropylperoxydicarbonate, di-sec-butylperoxydicarbonate, 1,1,3,3- Tetramethylbutyl peroxy neodecanoate, di (4-t-butylcyclohexyl) peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, t-hexyl peroxy neodecanoate, t-butylperoxy Neodecanoate, t-butylperoxy neoheptanoate, t-hexyl peroxy pivalate, t-butyl peroxy pivalate, di (3,5,5-trimethylhexanoyl peroxide, dilauroyl peroxide , 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, disuccinic acid peroxide, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane , t-hexyl peroxy-2-ethylhexanoate, di (4-methylbenzoyl) peroxide, t-butylperoxy-2-ethylhexanoate, di (3-methylbenzo Peroxide, benzoyl (3-methylbenzoyl) peroxide, dibenzoylperoxide, 1,1-di (t-butylperoxy) -2-methylcyclohexane, 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-butylperoxy) cyclohexane, 2,2-bis [4,4-di (t-butylperoxy) cyclohexyl] propane, t Hexyl peroxy isopropyl monocarbonate, t-butyl peroxy maleic acid, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxy laurate, t-butyl peroxy isopropyl Monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, 2 , 2-di (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl-4,4-di (t-butylperoxy) valerate, di (t-butylperoxyisopropyl) Benzene, dicumylperoxide, di (t-hexyl) peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butyl Milperoxide, di-t-butylperoxide, p-mentane hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, diisopropylbenzenehydroperoxide, 1, 1,3,3- tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, etc. are mentioned.

These radical polymerization initiators may be used individually by 1 type, and may be used in combination of 2 or more type. Although there is no restriction | limiting in particular in the compounding quantity of these hardening | curing agents, It is preferable to mix | blend 0.1-10 mass parts with respect to 100 mass parts of curable resin compositions, and it is more preferable to mix | blend 0.5-5 mass parts. When the compounding quantity of a hardening | curing agent is less than 0.1 mass part, it is difficult to obtain a sufficient hardening rate, and when a compounding quantity exceeds 10 mass parts, final hardened | cured material may fall and mechanical strength may fall.

Although the viscosity of curable resin composition of this invention is suitably adjusted with film thickness, it is preferable that it is 100-10000 mPa * s at 25 degreeC, 200-5000 mPa * s is more preferable, 500-3000 mPa * s is still more preferable. Do. If the viscosity is too low, the film film thickness precision tends to be lowered, and if too high, the equipment load increases. Moreover, when using high viscosity resin, you may make it low viscosity by heating.

Moreover, it can add to curable resin composition as needed, such as a ultraviolet absorber, antioxidant, a lubricating agent, in the range which does not impair the characteristic of this invention, such as transparency, heat resistance, and low birefringence.

There is no restriction | limiting in particular as antioxidant, What is generally used can be used. Among them, phenolic antioxidants, amine antioxidants, sulfur antioxidants, phosphorus antioxidants and the like are preferable, phenolic antioxidants and amine antioxidants which are radical chain inhibitors are more preferred, and phenolic antioxidants are particularly preferred. . As a phenolic antioxidant, 2, 6- di- t- butyl- p- cresol, 4, 4- butylidene bis- (6-t- butyl- 3-methyl phenol), 2, 2'- methylene bis (4 -Methyl-6-t-butylphenol), 2,2'-methylenebis- (4-ethyl-6-t-butylphenol), 2,6-di-t-butyl-4-ethylphenol, 1,1 , 3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate , Tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, triethylene glycol bis [3- (3-t-butyl-4-hydroxy- 5-methylphenyl) propionate], tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 4,4-thiobis- (6-t-butyl-3-methylphenol ), 3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl)] propionyloxy] -1,1'-dimethylethyl] -2,4,8, 10-tetraoxaspiro [5,5] undecane, thiodiethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N'-hexane-1 , 6-diylbis [3- (3,5-di-t-part And the like can be mentioned 4-hydroxyphenyl) propionamide]. Examples of the amine antioxidants include alkyldiphenylamine, N, N'-di-sec-butyl-p-phenylenediamine, N-phenyl-N'-1,3-dimethylbutyl-p-phenylenediamine and dialkylhydrides. And oxylamine. Examples of sulfur-based antioxidants include dilauryl-3,3'-thiodipropionate, ditridecyl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, and distea Reel-3,3'- thiodipropionate, pentaerythritol tetrakis (3-lauryl thio propionate), etc. are mentioned. Examples of phosphorus antioxidants include tris [2-[[2,4,8,10-tetra-t-butylbenzo [d, f] [1,3,2] dioxaphosphine-6-yl] oxy] ethyl] amine , Bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethylester phosphoric acid, tetrakis (2,4-di-t-butylphenyl) [1,1-biphenyl] -4, 4'- diyl bisphosphite etc. are mentioned. One type of these antioxidants may be used, or two or more types thereof may be used in combination.

There is no restriction | limiting in particular as a lubricant, What is generally used can be used. Especially, metal soap type lubricant, fatty acid ester type lubricant, aliphatic hydrocarbon type lubricant, etc. are preferable, and metal soap type lubricant is especially preferable. Examples of the metal soap-based lubricant include barium stearate, calcium stearate, zinc stearate, magnesium stearate and aluminum stearate. These may be used as a composite.

There is no restriction | limiting in particular as a ultraviolet absorber, What is generally used can be used. Especially, a benzophenone type ultraviolet absorber, a benzotriazole type ultraviolet absorber, and a cyanoacrylate type ultraviolet absorber are preferable, and a benzophenone type ultraviolet absorber is especially preferable. As the benzophenone ultraviolet absorber, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-butylphenyl) benzotriazole and 2- (2-hydroxy -3'-t-butylphenyl) benzotriazole etc. are mentioned.

As other additives, antifoaming agents, leveling agents, mold release agents, water repellents, flame retardants, low shrinkage agents, crosslinking aids, inorganic fillers, etc., for the purpose of improving hardness, strength, moldability, durability, and water resistance, are also used within the scope of not impairing the object or effect of the present invention. It can be used as needed.

The cured film obtained by the present invention preferably has a total light transmittance of 85% or more, more preferably 88% or more, still more preferably 91% or more, from the viewpoint of transparency in the range of 0.5 to 1.5 mm in thickness. Moreover, it is preferable that the haze value mentioned later is 1.5% or less, 1% or less is more preferable, and 0.8% or less is further more preferable. It is preferable that the birefringence value mentioned later is 10 nm or less, more preferably 5 nm or less, and still more preferable 3 nm or less from the viewpoint of applying the cured film of this invention as an optically isotropic material of glass replacement.

The cured film of this invention can be used suitably for optical materials, especially a mobile phone window (front plate), a cover for touch panels, a touch panel board | substrate, a transparent printed board, 3D glasses, etc.

Example

Although the present invention will be specifically described by the following synthesis examples, examples and comparative examples, the present invention is not limited to these descriptions.

The total light transmittance, haze, and birefringence of the films described in Examples and Comparative Examples were measured by the following method.

[Total light transmittance]

The total light transmittance was measured in accordance with JIS K-7361-1 using a fully automatic haze meter TC-H3DPK manufactured by Tokyo Denshoku Co., Ltd.

[Hayes]

Haze value was measured based on JISK-7136 using the fully automated haze meter TC-H3DPK by Tokyo Denshoku Co., Ltd.

[Birefringence]

Birefringence measured the in-plane birefringence (Re) in wavelength 589nm using OTSka Electronics Co., Ltd. RETS-1000.

Synthesis Example 1 Synthesis of Allyl Ester Resin

750 g (2.98 mol) of 1,4-cyclohexanedicarboxylic acid diallyl, 100 g (0.75 mol) of trimethylolpropane and dibutyl in a 1 L four-necked flask equipped with a stirrer, reflux condenser, gas introduction tube and thermometer 0.70 g of tin oxide was injected and heated while distilling off the alcohol (allyl alcohol) produced | generated at 180 degreeC under nitrogen stream. When the distilled alcohol became about 75 g, the inside of the reaction system was gradually depressurized to 6.6 kPa over about 4 hours, and the outflow rate of alcohol was accelerated. When almost no effluent came out, the reaction system was depressurized to 0.5 kPa and allowed to react for further 1 hour before the reaction was cooled. The reactant obtained by this is called "allyl ester resin."

Synthesis Example 2 Synthesis of Acrylate Oligomer

In a 1 L four-necked flask equipped with a stirrer, reflux condenser, gas introduction tube, and thermometer, 344 g (1 mol) of caprolactone-modified 2-hydroxyethyl acrylate (Fraccel FA2D from Daicel Corporation) and 148 g of phthalic anhydride ( 1 mol), 1.5 g of triphenylphosphine and 0.15 g of p-methoxyphenol were added, the mixture was stirred while bubbling air, heated to 90 ° C and reacted for 90 minutes, confirming that the acid value became approximately 109 mgKOH / g. The first reaction was completed.

Subsequently, 185g (0.5mol) of bisphenol-A epoxy resin (made by Asahi Kasei Corporation: EER-2603, epoxy equivalent = 185), 0.7g of triphenylphosphines and 0.07g of p-methoxyphenol were added, and it is 120 degreeC It heated up and reacted until the acid value became 5 mgKOH / g or less. The reactant obtained by this is called "acrylate oligomer."

Example 1:

80 parts by mass of allyl ester resin, 10 parts by mass of acrylate oligomer, 10 parts by mass of trimethylolpropane triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., `` NK ester A-TMPT ''), a photoinitiator (chiba specialty chemical) Made by Suzu Corporation, "DAROCUR MBF") 1.5 parts by mass, the thermal initiator (NOF CORPORATION, "Perhexyl I") 1 part by mass, and the viscosity (measured using a No. 3 rotor on a type B viscometer at 25 ° C) Curable resin composition (R1) which is 1800 mPa * s was prepared. This curable resin composition was apply | coated so that thickness might become thickness of 300 micrometers on PET film (50 micrometers in thickness) with a knife coater, and the curable resin layer was formed. Furthermore, PET film (50 micrometers in thickness) was laminated on curable resin layer as a cover film, and it hardened | cured by UV irradiation amount 600mJ / cm <2> (irradiation from 300mJ / cm <2> / 2 sides), and gel fraction (about 1 g of films obtained by hardening) And the cured film (F1) whose ratio with respect to the mass before extraction of the film mass after performing acetone reflux for 3 hours) was 58%. Two such laminated bodies were prepared.

Next, curable resin composition (R1) was apply | coated so that it may become thickness of 200 micrometers on the cured film (F1) surface which peeled off the PET film of one side of one laminated body, and a curable resin layer was formed, and the other laminated body After laminating the cured film (F1) surface which peeled off the PET film of single side | surface on the curable resin layer, it hardened | cured by UV irradiation amount 600mJ / cm <2> (irradiation from 300mJ / cm <2> / 2 sides), and it is set as cured film (F2), Moreover, it hardened completely by heat processing at 160 degreeC for 1 hour, the base PET film was peeled off, and the cured film (F3) of about 800 micrometers in thickness of approximately 100 mm x 150 mm shape was obtained. The thickness of the cured film was measured at four corners and at five center points using a digital micrometer (MDC-25MJ) manufactured by Mitutoyo Corporation, and obtained as the average value. The obtained cured film (F3) was cut out into a shape of 55 mm x 55 mm, and total light transmittance, haze, and birefringence (Re) were measured based on the above-described measuring method, and the total light transmittance was 91.8%, haze 0.8%, and birefringence ( Re) 2.7 nm.

Example 2:

80 mass parts of allyl ester resin, 20 mass parts of trimethylol propane triacrylates (made by Shin-Nakamura Chemical Co., Ltd., "NK ester A-TMPT"), and a photoinitiator (chiba specialty chemical) to curable resin composition (R1) Curable resin composition which consists of 1.5 mass parts of products made from "ZROCUR MBF"), 1 mass part of thermal initiators (NOF CORPORATION, "perhexyl I"), and has a viscosity (measured by a type B viscometer at 25 ° C) of 2500 mPa · s. Except having changed into (R2), it carried out similarly to Example 1, and obtained the cured film (F4) of about 800 micrometers in thickness which is 49% of gel fractions. The obtained cured film (F4) was 92.1% of total light transmittance, 0.7% of haze, and 2.3 nm of birefringence (Re).

Example 3:

Except having changed the curable resin composition apply | coated to cured film (F1) into curable resin composition (R2), it carried out similarly to Example 1, and obtained the cured film (F5) of about 800 micrometers in thickness. The obtained cured film (F5) was 92.0% of the total light transmittance, 0.8% of haze, and 2.2 nm of birefringence (Re).

Comparative Example 1:

Curable resin composition (R1) was apply | coated so that thickness might be about 800 micrometers on PET film (50 micrometers in thickness) with a knife coater, and the curable resin layer was formed. In addition, as a cover film, the same PET film as described above was laminated on the curable resin layer, and then cured at a UV irradiation amount of 1000 mJ / cm 2 (500 mJ / cm 2 × 2 / both sides), resulting in distortion, resulting in smooth measurement of optical properties. One film could not be obtained.

Claims (13)

The agent which apply | coats curable resin composition (A) to the surface of a 1st base material, forms a 1st curable resin layer, irradiates an energy ray to the said 1st curable resin layer, and obtains the 1st laminated body which formed the cured film (I). 2nd lamination | stacking which apply | coated curable resin composition (B) to 1st process and the surface of a 2nd base material, forms a 2nd curable resin layer, and irradiated the energy beam to the said 2nd curable resin layer, and formed the cured film (II). The 2nd process of obtaining a sieve, and the cured film (I) of the said 1st laminated body, and the cured film (II) of the said 2nd laminated body were bonded through the 3rd curable resin layer which consists of curable resin composition (C). The 3rd process of obtaining a 3rd laminated body by irradiating an energy beam afterwards, and hardening a 3rd curable resin layer, and peeling the said 1st base material and a 2nd base material from the said 3rd laminated body, and hardening with the said cured film (I) Obtaining laminated cured film (III) of film (II) Process for producing a cured film comprising the fourth step. The method of claim 1,
In the first and / or second step, the step of attaching a cover film to the surface of the first and / or second curable resin layer before irradiating an energy ray to the first and / or second curable resin layer. The method further includes a step of peeling the cover film before applying the curable resin composition (C) in the third step. 3. The method according to claim 1 or 2,
Bonding via the 3rd curable resin layer of the cured film (I) and cured film (II) in the said 3rd process apply | coats the said curable resin composition (C) on the said cured film (I), and is 3rd curable A method for producing a cured film, comprising a step of forming a resin layer, attaching the cured film (II) to the third curable resin layer, and irradiating an energy ray to cure the third curable resin layer. The method according to any one of claims 1 to 3,
The said 3rd process further includes the process of heat-processing after irradiation with an energy ray, The manufacturing method of the cured film characterized by the above-mentioned. The method according to any one of claims 1 to 4,
And a step of cutting the third laminate to a desired dimension by a laser before the fourth step. 6. The method according to any one of claims 1 to 5,
Said cured film (I) and cured film (II) are semi-hardened films, The manufacturing method of the cured film characterized by the above-mentioned. 7. The method according to any one of claims 1 to 6,
Said cured film (I) and cured film (II) are the same film thickness manufactured by the same composition and conditions, The manufacturing method of the cured film characterized by the above-mentioned. The method according to any one of claims 1 to 7,
The thickness of the said laminated cured film (III) is 0.5-1.5 mm, The manufacturing method of the cured film characterized by the above-mentioned. The method according to any one of claims 1 to 8,
The composition of the said curable resin composition (A), curable resin composition (B), and curable resin composition (C) is the same, The manufacturing method of the cured film characterized by the above-mentioned. 10. The method according to any one of claims 1 to 9,
Said curable resin composition (A), curable resin composition (B), and curable resin composition (C) contain an allyl ester resin and a photoinitiator, The manufacturing method of the cured film characterized by the above-mentioned. 11. The method of claim 10,
Said curable resin composition (A), curable resin composition (B), and curable resin composition (C) further contain a thermal initiator, The manufacturing method of the cured film characterized by the above-mentioned. 12. The method according to any one of claims 1 to 11,
The viscosity at 25 degrees C of the said curable resin composition (A), curable resin composition (B), and curable resin composition (C) is 100-10000 mPa * s, The manufacturing method of the cured film characterized by the above-mentioned. It was manufactured by the manufacturing method of the cured film of any one of Claims 1-12, The cured film characterized by the above-mentioned.