JP2011203560A - Antireflective laminate and method for producing the same, and curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition from which a cured film excellent in low refractive index property and scratch resistance is formed in a one-time application process, or to provide a method for producing an antireflective laminate having the cured film.SOLUTION: The method for producing an antireflective laminate includes steps of: (a) applying a curable composition containing at least (A) a polymerizable compound, (B) particles 22 having a refractive index of 1.40 or less and (D) a solvent on a cellulose resin substrate 10; (b) forming a cured film 20 on the cellulose resin substrate 10 by curing the curable composition, wherein the particles 22 are unevenly distributed in the cured film 20, the particles distributed close to the face opposite to the face in contact with the cellulose resin substrate 10. The solvent (D) contains a solvent (D1) that dissolves the cellulose resin of the substrate and has a boiling point of 80°C or higher and 250°C or lower under the pressure of 0.1 MPa, by 3 mass% or more and 100 mass% or less.

Description

  The present invention relates to an antireflection laminate, a method for producing the same, and a curable composition used in forming the antireflection laminate.

  In recent years, liquid crystal display devices have been used as display devices for televisions, personal computers, and the like. In such a liquid crystal display device, it has been proposed to use an antireflection film containing a low refractive index layer in order to prevent reflection of external light and improve image quality.

  An antireflection film used in a conventional liquid crystal display device has low refractive index properties and scratch resistance by applying a multilayer coating of a low refractive index layer and a hard coat layer. The antireflection film having such a multilayer structure can reduce the reflectance in the low refractive index layer, but has a problem that the productivity and cost are inferior because of the multilayer structure. Furthermore, the antireflection film produced by laminating the low refractive index layer and the hard coat layer has a problem that peeling easily occurs at the interface between the low refractive index layer and the hard coat layer.

  In order to solve such problems, a method for producing an antireflection film is proposed in which silica particles are modified with fluorine silane, and the silica particles are unevenly distributed in the liquid by surface energy, and then a cured film is formed. (For example, refer to Patent Document 1).

Japanese Patent No. 3861562

  However, the method described in Patent Document 1 has a problem that not only the uneven distribution of silica particles is insufficient and low refractive index is not obtained, but also the scratch resistance on the surface of the cured film is not excellent.

  Therefore, some embodiments according to the present invention provide a curable composition that can form a cured film excellent in low refractive index and scratch resistance by a single coating step by solving the above-described problems, or A method for producing an antireflection laminate having the cured film is provided.

  SUMMARY An advantage of some aspects of the invention is to solve at least a part of the problems described above, and the invention can be implemented as the following aspects or application examples.

[Application Example 1]
One aspect of the method for producing an antireflection laminate according to the present invention is as follows.
(A) applying a curable composition containing (A) a polymerizable compound, (B) particles having a refractive index of 1.40 or less, and (D) a solvent on a cellulose resin substrate;
(B) curing the curable composition to form a cured film on the cellulose resin substrate;
In the cured film, a method for producing an antireflection laminate in which the particles are unevenly distributed on the surface opposite to the surface in contact with the cellulose resin substrate,
(D) In 100% by mass of the solvent, (D1) 3% by mass or more and 100% by mass or less of a solvent that dissolves the cellulose resin of the base material and has a boiling point at 0.1 MPa of 80 ° C. or higher and 250 ° C. or lower It is characterized by doing.

[Application Example 2]
In application example 1,
Between the steps (a) and (b),
The method may further include a step of heating the curable composition.

[Application Example 3]
In application example 2,
The heating temperature can be lower than the boiling point of the component (D1).

[Application Example 4]
In any one of Application Examples 1 to 3,
The (B) particles may be hollow silica particles.

[Application Example 5]
In any one of Application Examples 1 to 4,
The cellulose resin base material may be a triacetyl cellulose base material.

[Application Example 6]
In any one of Application Examples 1 to 5,
The component (D1) can be at least one selected from propylene glycol monomethyl ether, ethyl lactate, N-methyl-2-pyrrolidone and γ-butyrolactone.

[Application Example 7]
One aspect of the curable composition according to the present invention is:
(A) a polymerizable compound, (B) particles having a refractive index of 1.40 or less, and (D) a solvent,
(D) In 100% by mass of the solvent, (D1) 3% by mass or more and 100% by mass or less of a solvent that dissolves the cellulose resin of the base material and has a boiling point at 0.1 MPa of 80 ° C. or higher and 250 ° C. or lower To do.

[Application Example 8]
In Application Example 7,
The (B) particles may be hollow silica particles.

  According to the method for producing an antireflection laminate according to the present invention, the surface opposite to the surface in contact with the cellulose resin substrate is obtained by once applying and curing the curable composition on the cellulose resin substrate. A layer in which particles having a refractive index of 1.40 or less are present at a high density on the side, and a layer in which particles having a refractive index of 1.40 or less are not substantially present on the side in contact with the cellulose resin substrate Can be formed. As a result, an antireflection laminate having both scratch resistance and low refractive index can be produced.

It is sectional drawing which showed typically the laminated body for reflection manufactured with the manufacturing method of the laminated body for reflection which concerns on this Embodiment.

  Hereinafter, preferred embodiments according to the present invention will be described in detail. In addition, this invention is not limited to the following embodiment, Various modifications implemented in the range which does not change the summary of this invention are also included.

1. Curable composition The curable composition which concerns on this Embodiment contains (A) polymeric compound, (B) particle | grains whose refractive index is 1.40 or less, and (D) solvent at least. Hereinafter, each component of the curable composition which concerns on this Embodiment is demonstrated in detail. In the following description, the materials (A) to (D) may be abbreviated as components (A) to (D), respectively.

1.1. (A) Polymerizable compound The curable composition which concerns on this Embodiment contains (A) polymeric compound. (A) A component is a main component which forms a cured film.

  The component (A) is not particularly limited as long as it contains two or more polymerizable groups in the molecule, and examples thereof include (meth) acrylic ester compounds, vinyl compounds, epoxy compounds, and alkoxymethylamine compounds. (Meth) acrylic ester compounds are preferred.

  (Meth) acrylic ester compounds include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) Acrylate, dipentaerythritol hexa (meth) acrylate, glycerin tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethylene glycol di (meth) acrylate, 1,3-butanediol di ( (Meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate Hydroxyl group-containing compounds such as diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate ) Acrylates and poly (meth) acrylates of ethylene oxide or propylene oxide adducts to these hydroxyl groups, oligoesters (meth) acrylates having two or more (meth) acryloyl groups in the molecule, oligoethers (meth) Examples include acrylates and oligoepoxy (meth) acrylates. Among these, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate and the like are preferable. .

  Examples of vinyl compounds include divinylbenzene, ethylene glycol divinyl ether, diethylene glycol divinyl ether, and triethylene glycol divinyl ether.

  As epoxy compounds, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, glycerin triglycidyl ether, etc. Can be mentioned.

  Examples of the alkoxymethylamine compound include hexamethoxymethylated melamine, hexabutoxymethylated melamine, tetramethoxymethylated glycoluril, tetrabutoxymethylated glycoluril and the like.

  Examples of commercially available products of such component (A) include, for example, Aronix M-400, M-404, M-408, M-450, M-305, M-309, M-310, manufactured by Toagosei Co., Ltd. M-315, M-320, M-350, M-360, M-208, M-210, M-215, M-220, M-225, M-233, M-240, M-245, M- 260, M-270, M-1100, M-1200, M-1210, M-1310, M-1600, M-221, M-203, TO-924, TO-1270, TO-1231, TO-595, TO-756, TO-1343, TO-902, TO-904, TO-905, TO-1330, KAYARAD D-310, D-330, DPHA, DPCA-20, DPCA manufactured by Nippon Kayaku Co., Ltd. 30, DPCA-60, DPCA-120, DN-0075, DN-2475, SR-295, SR-355, SR-399E, SR-494, SR-9041, SR-368, SR-415, SR-444, SR-454, SR-492, SR-499, SR-502, SR-9020, SR-9035, SR-111, SR-212, SR-213, SR-230, SR-259, SR-268, SR- 272, SR-344, SR-349, SR-601, SR-602, SR-610, SR-9003, PET-30, T-1420, GPO-303, TC-120S, HDDA, NPGDA, TPGDA, PEG400DA, MANDA, HX-220, HX-620, R-551, R-712, R-167, R-526, R-5 51, R-712, R-604, R-684, TMPTA, THE-330, TPA-320, TPA-330, KS-HDDA, KS-TPGDA, KS-TMPTA, light acrylate PE-manufactured by Kyoeisha Chemical Co., Ltd. 4A, DPE-6A, DTMP-4A and the like. These compounds may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  In the curable composition which concerns on this Embodiment, content of (A) polymeric compound is 80 mass% or more normally, when the sum total of the component except a solvent is 100 mass%, Preferably it is 90. It is at least mass%. This is because if the amount added is less than 80% by mass, sufficient hardness may not be obtained.

1.2. (B) Particles with Refractive Index of 1.40 or Less The curable composition according to the present embodiment contains (B) particles with a refractive index of 1.40 or less. When such particles are unevenly distributed on the surface of the cured film, a low refractive index layer can be formed, and the function as an antireflection film can be imparted to the cured film. In addition, since the particles are unevenly distributed on the surface of the cured film, the effects of improving the hardness of the surface of the cured film and reducing the curl are also expected.

  The refractive index of the particles is 1.40 or less, preferably 1.35 or less, more preferably 1.30 or less. The reason for setting the refractive index to 1.40 or less is that a cured film having excellent antireflection properties cannot be obtained even if particles having a refractive index exceeding 1.40 are added. Further, the refractive index is preferably as low as possible with 1.00 being the lower limit. However, when hollow particles are used, the strength of the cured film and the scratch resistance are reduced because the strength of the particles decreases as the refractive index decreases. . Therefore, the lower limit of the refractive index is preferably 1.20. The “refractive index” in this specification refers to the refractive index of Na-D line (wavelength 589 nm) at 25 ° C. In the present specification, “refractive index of particles” means that a composition in which the content of particles in a solid content is 1% by mass, 10% by mass, and 20% by mass is formed in the same matrix, The refractive index at the Na-D line at 25 ° C. is measured, and the particle content is 100% by mass calculated by the calibration curve method.

  The particles are not particularly limited as long as the refractive index is 1.40 or less, and examples thereof include hollow silica particles and metal fluoride particles. Among these, hollow silica particles mainly composed of silica are preferable. Since the hollow silica particles have cavities inside, the refractive index can be further reduced as compared with the solid particles.

  The number average particle diameter of the particles measured with a transmission electron microscope is preferably 1 to 100 nm, more preferably 5 to 60 nm. The shape of the particles is not limited to a spherical shape, and may be an irregular shape.

  Examples of commercially available hollow silica particles include “JX1008SIV” manufactured by JGC Catalysts & Chemicals Co., Ltd. (number average particle diameter 50 nm, solid content 20% by mass, isopropyl alcohol solvent obtained with a transmission electron microscope), “JX1009SIV” ( And a number average particle diameter of 50 nm, a solid content of 20% by mass, and a methyl isobutyl ketone solvent) obtained with a transmission electron microscope.

  The hollow silica particles used in the present embodiment may be modified with a particle modifier. Examples of the particle modifier include compounds having a polymerizable unsaturated group and a hydrolyzable silyl group (hereinafter also referred to as “polymerizable particle modifier”). Examples of the polymerizable unsaturated group of the polymerizable particle modifier include a vinyl group and a (meth) acryloyl group. The hydrolyzable silyl group is a group that reacts with water to produce a silanol group (Si—OH). For example, one or more methoxy groups, ethoxy groups, n-propoxy groups, isopropoxy groups on silicon. A group, an alkoxyl group such as an n-butoxy group, an aryloxy group, an acetoxy group, an amino group, or a halogen atom is bonded.

  As the polymerizable particle modifier used in the present embodiment, a commercially available product such as methacryloyloxypropyltrimethoxysilane can be used, for example, a compound described in International Publication No. WO97 / 12942 is used. You can also.

  In addition, a fluorine-containing hydrolyzable silyl group-containing compound (hereinafter also referred to as “fluorine-containing particle modifier”) can be used as the particle modifier. By using the fluorine-containing particle modifier, it is possible to efficiently distribute the hollow silica particles. Commercially available products such as tridecafluorooctyltrimethoxysilane can be used as the fluorine-containing particle modifier used in the present embodiment.

  Moreover, the particle modifier which has an alkyl group, and the particle modifier which has a silicone chain can be used similarly to a fluorine-containing particle modifier.

  The above various particle modifiers may be used alone or in combination of two or more.

  In order to modify the hollow silica particles used in the present embodiment, the hollow silica particles and the particle modifier may be mixed and hydrolyzed to bond them together. The ratio of the organic polymer component, that is, the hydrolyzate and condensate of hydrolyzable silane, in the obtained reactive hollow silica particles is usually the weight loss when the dry powder is completely burned in air. The constant value of can be determined, for example, by thermogravimetric analysis from room temperature to usually 800 ° C. in air.

  The binding amount of the particle modifier to the reactive hollow silica particles is preferably 0.01 to 40% by mass, more preferably 0.1 to 30% by mass, when the modified hollow silica particles are 100% by mass. %, Particularly preferably 1 to 20% by mass. By setting the amount of the particle modifier to react with the hollow silica particles in the above range, not only can the dispersibility of the hollow silica particles in the composition be improved, but also the transparency and scratch resistance of the resulting cured product can be improved. The effect of increasing can be expected.

  In the curable composition which concerns on this Embodiment, content of (B) component can be suitably adjusted according to the film thickness of the cured film to form. For example, when the thickness of the cured film is 10 μm, when the total of the components excluding the solvent is 100% by mass, preferably 0.4 to 1.2% by mass, more preferably 0.5 to 1% by mass. Within range. For example, when the thickness of the cured film is 7 μm, it is preferably 0.6 to 1.8% by mass, more preferably 0.7 to 1.5% by mass, and preferably when the thickness of the cured film is 3 μm. Is in the range of 1.2 to 4 mass%, more preferably 1.5 to 3 mass%. When the content of the component (B) is less than the above range, it may be impossible to form a layer (low refractive index layer) in which the component (B) that exhibits antireflection properties exists at a high density. On the other hand, if the content of the component (B) exceeds the above range, the thickness of the layer (low refractive index layer) in which the component (B) that exhibits antireflection properties is present at a high density becomes too large and reflection The rate reduction effect may not appear.

1.3. (C) Polymerization initiator The curable composition concerning this Embodiment may contain (C) polymerization initiator. As such (C) polymerization initiator, when (meth) acrylic ester compound and / or vinyl compound is contained as component (A), a compound (thermal polymerization initiator) that generates active radical species thermally. And general-purpose products such as compounds (radiation (light) radical polymerization initiators) that generate active radical species upon irradiation with radiation (light). In addition, when an epoxy compound and / or an alkoxymethylamine compound is contained as the component (A), general-purpose products such as an acidic compound and a compound (radiation (light) acid generator) that generates an acid upon irradiation with radiation (light) Can be mentioned. Among these, a radiation (photo) polymerization initiator is preferable.

  The radiation (photo) radical polymerization initiator is not particularly limited as long as it can be decomposed by light irradiation to generate radicals to initiate polymerization. For example, acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone 2,2-dimethoxy-1,2-diphenylethane-1-one, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4′-dimethoxy Benzophenone, 4,4′-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2- Morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone) and the like.

  Commercially available products of radiation (photo) radical polymerization initiators include, for example, Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI1700, CGI1750, CGI1850, CG24-61, Darocur, manufactured by Ciba Japan Co., Ltd. 1116, 1173, BASF's Lucillin TPO, 8893UCB's Ubekrill P36, Lamberti's Ezacure KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75 / B, and the like.

  The thermal radical polymerization initiator is not particularly limited as long as it is decomposed by heating to generate radicals to initiate polymerization, and examples thereof include peroxides and azo compounds. Specific examples include: Examples include benzoyl peroxide, t-butyl-peroxybenzoate, and azobisisobutyronitrile.

  As the radiation (photo) acid generator, compounds of triarylsulfonium salts and diaryliodonium salts can be used. Examples of commercially available radiation (light) acid generators include CPI-100P and 101A manufactured by San Apro.

  In the curable composition according to the present embodiment, the content of the (C) polymerization initiator used as necessary is preferably 0.01 when the total of the components excluding the solvent is 100% by mass. -20 mass%, More preferably, it exists in the range of 0.1-10 mass%. If it is less than 0.01% by mass, the hardness of the cured product may be insufficient, and if it exceeds 20% by mass, the hardness of the coating film may be impaired. In addition, (C) a polymerization initiator can also use multiple types of compounds together.

1.4. (D) Solvent The curable composition according to this embodiment is used after being diluted with (D) a solvent in order to adjust the thickness of the coating film. For example, the viscosity when the curable composition according to the present embodiment is used as an antireflection film or a coating material is usually 0.1 to 50,000 mPa · sec / 25 ° C., preferably 0.5 to 10, 000 mPa · sec / 25 ° C.

  In the solvent (D) used in the present embodiment, (D1) a solvent that dissolves the cellulose resin of the base material and has a boiling point at 0.1 MPa of 80 ° C. or higher and 250 ° C. or lower (hereinafter referred to as (D1) Also referred to as an ingredient). In the present invention, “dissolving the cellulose resin of the base material” means that when a 80 μm-thick cellulose resin film cut into a size of 18 cm × 1 cm is immersed in 6 g of solvent for 2 hours, the mass of the film decreases. The rate is 2% or more.

  Examples of such component (D1) include propylene glycol monomethyl ether, ethyl lactate, N-methyl-2-pyrrolidone, and γ-butyrolactone. The solubility of each compound shown here in triacetyl cellulose and the boiling point at 0.1 MPa are as shown in Table 1 shown in the following examples, and all the compounds satisfy the conditions of the component (D1). It is. These compounds may be used alone or in combination of two or more.

  Since the curable composition according to the present embodiment contains the component (D1), the component (D1) having a high affinity with the cellulose resin substrate at the time of heating and drying is attracted to the cellulose resin substrate side. As a result, it is considered that the component (B) is unevenly distributed at the interface opposite to the cellulose resin base material.

  As will be described later, in the method for producing an antireflection laminate according to the present embodiment, the curable composition according to the present embodiment is applied to a cellulose resin substrate, and then usually heated and dried at 80 to 120 ° C. A process is performed. Here, when the boiling point at 0.1 MPa of the solvent having solubility in the cellulose resin is less than 80 ° C., the solvent evaporates at the time of this heat drying, so that the uneven distribution of the component (B) does not occur. On the other hand, if the boiling point at 0.1 MPa is higher than 250 ° C., the solvent remains in the cured film, which may cause a decrease in hardness. For these reasons, the boiling point at 0.1 MPa of the component (D1) is 80 ° C. or higher and 250 ° C. or lower, preferably 100 ° C. or higher and 240 ° C. or lower, more preferably 120 ° C. or higher and 220 ° C. or lower.

  Examples of the solvent other than the component (D1) include alcohols such as methanol, ethanol, isopropanol, butanol and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethyl acetate, butyl acetate and ethyl lactate. , Γ-butyrolactone, esters such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbons such as benzene, toluene and xylene; dimethylformamide And amides such as dimethylacetamide and N-methylpyrrolidone.

  In the curable composition which concerns on this Embodiment, content of (D) solvent is in the range of 50-10,000 mass parts, when the sum total of the component except (D) solvent is 100 mass parts. Preferably there is. The content of the solvent can be appropriately determined in consideration of the coating film thickness, the viscosity of the curable composition, and the like.

  Moreover, in the curable composition which concerns on this Embodiment, the ratio of (D1) component in 100 mass% of (D) solvent is 3 mass% or more and 100 mass% or less, and 5 mass% or more and 100 mass% or less. It is preferable that (D) When the ratio of the component (D1) in 100% by mass of the solvent is less than 3% by mass, the uneven distribution of the component (B) described above is difficult to occur.

1.5. Other Additives The curable composition according to the present embodiment includes, as necessary, a particle dispersant, an antioxidant, an ultraviolet absorber, a light stabilizer, a silane coupling agent, an antiaging agent, and a thermal polymerization inhibitor. , Colorants, leveling agents, surfactants, storage stabilizers, plasticizers, lubricants, inorganic fillers, organic fillers, fillers, wettability improvers, coating surface improvers, and the like. Among these, by using a compound containing a fluorine atom or a compound having a siloxane chain as the particle dispersant, the uneven distribution of the hollow silica particles can be promoted, and the refractive index of the coating film can be lowered.

1.6. Manufacturing method of curable composition The curable composition which concerns on this Embodiment is (A) polymeric compound, (B) particle | grains, (D) solvent, (C) radical polymerization initiator as needed, other It can prepare by adding an additive, respectively, and mixing under room temperature or a heating condition. Specifically, it can prepare using mixers, such as a mixer, a kneader, a ball mill, and a three roll. However, when mixing under heating conditions, it is preferable to carry out at or below the decomposition temperature of the thermal polymerization initiator.

2. Antireflection laminate and production method thereof The production method of the antireflection laminate according to the present embodiment is as follows.
(A) applying a curable composition containing (A) a polymerizable compound, (B) particles having a refractive index of 1.40 or less, and (D) a solvent on a cellulose resin substrate;
(B) curing the curable composition to form a cured film on the cellulose resin substrate. In the method for producing an antireflection laminate according to this embodiment, (D1) the cellulose resin of the base material is dissolved in 100% by mass of the solvent, and the boiling point at 0.1 MPa is 80 ° C. or higher and 250 ° C. A solvent having a temperature of ℃ or less is contained in an amount of 3% by mass to 100% by mass.

  According to such a method for producing an antireflection laminate, once the curable composition is applied on a cellulose resin substrate and cured, the surface is refracted to the side opposite to the surface in contact with the cellulose resin substrate. A layer in which particles having a refractive index of 1.40 or less are present at a high density is formed, and a layer in which particles having a refractive index of 1.40 or less are not substantially present is formed on the side in contact with the cellulose resin substrate. be able to. As a result, an antireflection laminate having both scratch resistance and low refractive index can be produced. Hereinafter, it demonstrates for every process.

2.1. Step (a)
First, the curable composition mentioned above is prepared. Since the structure and manufacturing method of such a curable composition are as described above, detailed description thereof will be omitted.

  Next, the prepared curable composition is apply | coated on a cellulose resin base material. The application method is not particularly limited, and for example, bar coating, air knife coating, gravure coating, gravure reverse coating, reverse roll coating, lip coating, die coating, dip coating, offset printing, flexographic printing Known methods such as printing and screen printing can be used.

2.2. Step (b)
Next, the curable composition applied on the cellulose resin substrate is cured to form a cured film on the cellulose resin substrate. The curing conditions for the curable composition are not particularly limited. Specifically, after heat-treating at 0 to 200 ° C., preferably 80 to 120 ° C. to dry the volatile components, the antireflection laminate is formed by performing a curing treatment with radiation and / or heat. Can do. A preferable condition for curing with heat is 20 to 150 ° C., and is performed in a range of 10 seconds to 24 hours. When curing with radiation, it is preferable to use ultraviolet rays or electron beams. Irradiation light amount of the ultraviolet rays is preferably 0.01 to 10 J / cm ^2, more preferably 0.1~2J / cm ^2. Moreover, the irradiation conditions of an electron beam are a pressurization voltage of 10-300 kV, an electron density of 0.02-0.30 mA / cm < ² >, and an electron beam irradiation amount of 1-10 Mrad.

  As described above, it is preferable to further provide a step of heating the curable composition coated on the cellulose resin substrate between the step (a) and the step (b). By providing the heating step, the (D) solvent in the curable composition can be volatilized and removed. Since the solvent is removed by further providing the heating step (D), an antireflection laminate having excellent curability can be formed. Here, the heating temperature is 0 to 200 ° C., preferably 80 to 120 ° C., because of the relationship with the boiling point of the component (D1) described above, but it may be set lower than the boiling point of the component (D1). . This is because if the component (D1) is volatilized and removed quickly by heating at a temperature higher than the boiling point of the component (D1), the (B) particles are less likely to be unevenly distributed. The “heating temperature” means that the cellulose resin substrate coated with the curable composition is exposed to the atmosphere at the temperature, even if the cellulose resin substrate or the coating film does not reach the temperature. Good.

  The mechanism in which the (B) particles are unevenly distributed by applying and curing the curable composition once on the cellulose resin substrate will be described below. Since the component (D1) is present in the curable composition applied on the cellulose resin, a part of the cellulose resin as the base material is dissolved in the curable composition. Since the dissolved cellulose resin is hydrophilic, the applied curable composition has increased hydrophilicity in the vicinity of the substrate, and the relatively hydrophobic component (B) is unevenly distributed on the opposite side of the substrate. It is considered a thing.

2.3. Next, the antireflection laminate manufactured by the above-described method for manufacturing the antireflection laminate according to the present embodiment will be described. FIG. 1 is a cross-sectional view schematically showing an antireflection laminate produced by the method for producing an antireflection laminate according to the present embodiment. As shown in FIG. 1, in the antireflection laminate 100, a cured film 20 obtained by curing the above-described curable composition is formed on a cellulose resin substrate 10 as a substrate, and the cured film 20. Among them, a hard coat layer 24 substantially free of particles 22 is formed on the side in contact with the cellulose resin substrate 10, and the particles 22 are dense on the side opposite to the surface in contact with the substrate 10. A low refractive index layer 26 is formed. Hereinafter, each layer of the antireflection laminate according to the present embodiment will be described.

2.3.1. Base material The base material used for the laminated body for antireflection which concerns on this Embodiment is a cellulose resin base material. By using a cellulose resin as a base material, the component (D1) contained in the curable composition described above interacts with the cellulose resin base material, and the component (D1) is drawn to the surface side in contact with the cellulose resin base material. It is done. By this action, it is considered that the low refractive index layer 26 in which the particles 22 are present at a high density can be formed on the surface opposite to the surface in contact with the cellulose resin substrate. On the other hand, when a resin other than the cellulose resin is used as the base material, the above-described effects are not achieved. In the present embodiment, the cellulose resin base material may be a base material itself formed of a cellulose resin, or a base material having a cellulose resin layer on the surface of a base material such as polyethylene terephthalate or polycarbonate. . Here, examples of the cellulose resin that can be used as the base material include triacetyl cellulose, diacetyl cellulose, and cellulose acetate butyrate.

  In addition, the antireflection laminate having a base material made of cellulose resin is used in a wide range of hard coats and / or reflections such as a protective film for a polarizer in a camera lens unit, a television (CRT) screen display unit, or a liquid crystal display device. In the field of use of the anti-reflection film, excellent scratch resistance and antireflection effect can be obtained.

2.3.2. Hard Coat Layer The hard coat layer 24 is composed of a layer in which the particles 22 are not substantially present in the cured film 20 having a two-layer structure obtained by curing the curable composition described above.

  Although the thickness of the hard-coat layer 24 is not specifically limited, Preferably it is 1-50 micrometers, More preferably, it is 1-10 micrometers. If the thickness of the hard coat layer 24 is less than 1 μm, the hardness may be insufficient. On the other hand, if the thickness exceeds 50 μm, it is difficult to form a homogeneous film or the curling of the laminate is increased. This is because it may become difficult. In order to dissolve the cellulose resin when the curable composition is applied, the hard coat layer 24 may contain a cellulose resin component.

2.3.3. Low Refractive Index Layer The low refractive index layer 26 is composed of a layer in which particles 22 are present at a high density in the cured film 20 having a two-layer structure obtained by curing the curable composition described above.

  The thickness of the low refractive index layer 26 is not particularly limited, but is preferably 50 to 200 nm, more preferably 60 to 150 nm, and particularly preferably 80 to 120 nm. This is because if the thickness of the low refractive index layer 26 is less than 50 nm, a sufficient antireflection effect may not be obtained, whereas if it exceeds 200 nm, the antireflection effect may be reduced.

  The refractive index difference between the hard coat layer 24 and the low-refractive index layer 26 in the antireflection laminate 100 is preferably set to a value of 0.05 or more. This is because if the difference in refractive index between the hard coat layer 24 and the low refractive index layer 26 is less than 0.05, a synergistic effect in these antireflection films cannot be obtained, and the antireflection effect is lowered. Because there is a case to do.

3. EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

3.1. Example 1
3.1.1. Production of Curable Composition In a container shielded from ultraviolet rays, hollow silica particles (trade name “JX-1009SIV”, methyl isobutyl ketone sol, manufactured by JGC Catalysts & Chemicals Co., Ltd.) 96 parts by mass of pentaerythritol triacrylate (trade name “Kayarad PET-30”, manufactured by Nippon Kayaku Co., Ltd.), 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one ( Trade name “Irgacure (registered trademark) 907”, manufactured by Ciba Japan Co., Ltd.) 3 parts by mass, Silaplane FM0725 (produced by Chisso Corporation) 0.1 part by mass, 95 parts by mass of methyl isobutyl ketone, and 5 parts of γ-butyrolactone A homogeneous solution was obtained by adding part by mass and stirring at room temperature for 2 hours. 2 g of this solution was weighed in an aluminum dish, dried on a hot plate at 175 ° C. for 30 minutes, weighed, and the solid content was determined to be 50% by mass.

3.1.2. Preparation of cured film sample The solution obtained in the above "3.1.1. Production of curable composition" was placed on a triacetyl cellulose film (trade name "TDY-80UL", manufactured by Fuji Film Co., Ltd.) with a bar coater. It was applied so that the entire cured film thickness was about 7 μm, dried at 80 ° C. for 2 minutes, and then cured using a high-pressure mercury lamp (300 mJ / cm ² ) under a nitrogen flow. In addition, application | coating was performed so that a coating film might be formed in the inner surface of the film wound by roll shape.

3.2. Examples 2-11, Comparative Examples 1-3
A curable composition was produced in the same manner as in Example 1 except that the components shown in Table 2 or Table 3 were blended in the composition shown in Table 2 or Table 3, and a cured film sample was obtained. Table 1 summarizes data on the types of solvent components, solubility in triacetylcellulose (TAC), and boiling points. In addition, the presence or absence of the solubility with respect to triacetylcellulose was determined by the method mentioned above. That is, a triacetyl cellulose film obtained by immersing a 80 μm thick triacetyl cellulose film (trade name “TDY-80UL”, manufactured by FUJIFILM Corporation) in a size of 18 cm × 1 cm for 2 hours in 6 g of a solvent. When the mass reduction rate is 2% or more, it is determined that the solvent has solubility in the cellulose resin. When the mass reduction rate is less than 2%, the solvent is cellulose as a base material. The resin was judged not to dissolve.

  Moreover, the base material used in Example 9 and Example 10 was prepared by dissolving a cellulose acetate butyrate resin (trade name “CAB-381-20”, manufactured by Eastman Chemical Co., Ltd.) in acetone at 20 mass%. A base material in which a 5 μm cellulose resin film was formed on a polyethylene terephthalate and a polycarbonate base material using a bar coater and dried at 80 ° C. for 3 minutes was used. In addition, when the solubility of cellulose acetate butyrate in γ-butyrolactone was tested in the same manner, the solubility was high, and the base material collapsed during the pulling, so that no numerical value is shown.

  The particle “B-1” used in Example 11 was synthesized as follows. Hollow silica particles (trade name “JX-1009SIV”, methyl isobutyl ketone sol, manufactured by JGC Catalysts & Chemicals Co., Ltd.) 90.9 parts by mass (solid content concentration: 20 parts by mass), tridecafluorooctyltrimethoxysilane (GE Toshiba Silicone) (Made by Co., Ltd.) 1 part by mass, 0.1 part by mass of isopropanol and 0.05 part by mass of ion exchange water were stirred at 80 ° C. for 3 hours, and then 0.7 part by mass of methyl orthoformate was added. Further, colorless and transparent particle dispersion B-1 was obtained by heating and stirring at the same temperature for 1 hour. After weighing 2 g of B-1 in an aluminum dish, it was dried on a hot plate at 120 ° C. for 1 hour and weighed to determine the solid content, which was 22.5% by mass.

3.3. Evaluation test The characteristics of the curable compositions and cured films obtained in Examples and Comparative Examples were evaluated for the following items. The results are also shown in Table 2 and Table 3.

3.3.1. Reflectance The back surface of the obtained cured film was painted with black spray, and a spectral reflectance measurement device (a self-recording spectrophotometer U-3410 incorporating a large sample chamber integrating sphere attachment device 150-09090, manufactured by Hitachi, Ltd.) was used. The reflectance in the wavelength range of 340 to 700 nm was measured from the substrate side and evaluated. Specifically, the reflectance of the antireflection laminate (antireflection film) at each wavelength is measured using the reflectance of the aluminum deposited film as a reference (100%), and the reflectance of light at a wavelength of 550 nm is expressed. 2 and Table 3 are also shown. If the reflectance is less than 3%, it can be determined that the reflectance is low.

3.3.2. Scratch resistance (steel wool resistance test)
The obtained cured film is attached with steel wool (Bonster No. 0000, manufactured by Nippon Steel Wool Co., Ltd.) to a Gakushin type friction fastness tester (AB-301, manufactured by Tester Sangyo Co., Ltd.), and the surface of the cured film is loaded Scratching was repeated 10 times under the condition of 200 g, and the presence or absence of scratches on the surface of the cured film was visually confirmed according to the following criteria. The evaluation criteria are as follows.
AA: No damage occurs on the cured film.
A: Almost no peeling of the cured film or generation of scratches is observed, or slight thin scratches are observed on the cured film.
B: A streak is recognized on the entire surface of the cured film.
C: Separation of the cured film occurs.

3.3.3. Pencil hardness Based on "JIS K5600-5-4", the obtained cured film was fixed on a glass substrate and evaluated.

3.4. Evaluation results From the results of Tables 2 and 3, it was found that in the cured films obtained by curing the curable compositions of Examples 1 to 11, the reflectance was less than 3% and had antireflection properties. . Moreover, it turned out that it is excellent also in abrasion resistance from the result of steel wool resistance.

  On the other hand, from the results in Table 2, the cured films obtained by curing the curable compositions of Comparative Examples 1 to 3 are excellent in scratch resistance, but the reflectance exceeds 3% and is reflected. The rate was found to be inferior.

In the cured films of Examples 2, 3, 8 and Comparative Example 1, Raman spectroscopic measurement of the hard coat layer (manufactured by JEOL Ltd., using model “JRS-SYSTEM2000”) was performed. As a result, a peak at 1740 cm ⁻¹ derived from the carbonyl group of triacetyl cellulose was detected from the hard coat layers of Examples 2, 3 and 8, but from the hard coat layer of Comparative Example 1 to triacetyl cellulose. No derived peak was detected. That is, it was suggested that a part of the triacetyl cellulose as a base material was mixed in the hard coat layers of Examples 2, 3 and 8.

  The present invention is not limited to the above-described embodiments, and various modifications can be made. For example, the present invention includes substantially the same configuration (for example, a configuration having the same function, method, and result, or a configuration having the same purpose and effect) as the configuration described in the embodiment. In addition, the invention includes a configuration in which a non-essential part of the configuration described in the embodiment is replaced. In addition, the present invention includes a configuration that achieves the same effect as the configuration described in the embodiment or a configuration that can achieve the same object. In addition, the invention includes a configuration in which a known technique is added to the configuration described in the embodiment.

DESCRIPTION OF SYMBOLS 10 ... Cellulose resin base material, 20 ... Cured film, 22 ... Particle, 24 ... Hard coat layer, 26 ... Low refractive index layer

Claims (9)

(A) applying a curable composition containing (A) a polymerizable compound, (B) particles having a refractive index of 1.40 or less, and (D) a solvent on a cellulose resin substrate;
(B) curing the curable composition to form a cured film on the cellulose resin substrate;
In the cured film, a method for producing an antireflection laminate in which the particles are unevenly distributed on the surface opposite to the surface in contact with the cellulose resin substrate,
In (D) 100% by mass of the solvent, (D1) a solvent in which the base cellulose resin is dissolved and the boiling point at 0.1 MPa is 80 ° C. or more and 250 ° C. or less is 3% by mass or more and 100% by mass or less. A method for producing an antireflection laminate, comprising: In claim 1,
Between the steps (a) and (b),
The manufacturing method of the laminated body for antireflection which further includes the process of heating the said curable composition. In claim 2,
The method for producing an antireflection laminate, wherein the heating temperature is lower than the boiling point of the component (D1). In any one of Claims 1 to 3,
The method for producing an antireflection laminate, wherein the (B) particles are hollow silica particles. In any one of Claims 1 thru | or 4,
The said cellulose resin base material is a manufacturing method of the laminated body for reflection prevention which is a triacetyl cellulose base material. In any one of Claims 1 thru | or 5,
The component (D1) is a method for producing an antireflection laminate, wherein the component (D1) is at least one selected from propylene glycol monomethyl ether, ethyl lactate, N-methyl-2-pyrrolidone, and γ-butyrolactone. A laminate having a cured film of a curable composition containing (A) a polymerizable compound and (B) particles having a refractive index of 1.40 or less on a cellulose resin substrate,
In the cured film, the (B) particles having a refractive index of 1.40 or less are unevenly distributed on the surface opposite to the surface in contact with the cellulose resin substrate, and the cellulose resin component is present in the cured film. An antireflection laminate, comprising: (A) a polymerizable compound, (B) particles having a refractive index of 1.40 or less, and (D) a solvent,
(D) In 100% by mass of the solvent, (D1) 3% by mass or more and 100% by mass or less of a solvent that dissolves the cellulose resin of the base material and has a boiling point at 0.1 MPa of 80 ° C. or higher and 250 ° C. or lower A curable composition for forming an antireflection laminate, in which the particles are unevenly distributed on the side of the cured film opposite to the surface in contact with the substrate. In claim 8,
The said (B) particle | grain is a curable composition which is a hollow silica particle.

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