JP4435366B2 - Manufacturing method of laminate - Google Patents

Description

【００３６】
［比較例］
実施例１において使用したアニオン系高分子分散剤に替えてアニオン系界面活性剤型分散剤（ジオクチルスルホコハク酸ナトリウム<ラピゾールB80：日本油脂社>）を使用した以外、実施例１と同様にして比較例となる積層体を製造した。
【００３７】
以上の実施例１及び比較例の製造方法で得られた積層体の全光線透過率（ＪＩＳ−Ｋ７１０５）を、耐湿温促進試験（９０％ＲＨ、６０℃、１４０時間）を行う前後で測定した結果を表１に示す。
【００３８】
【表１】

【００３９】
表１からも明らかなように、実施例１の積層体１は耐湿温促進試験の前後で殆ど全光線透過率に変化が見られず、酸化珪素系薄膜の機能である反射防止効果が損なわれていなかったが、比較例の積層体は耐湿温促進試験後の全光線透過率が極めて低下し、酸化珪素系薄膜が消失して反射防止効果が失われてしまっていた。
【００４０】
［実施例２］
厚み６０μｍのポリプロピレンフィルム５（トレファンＢＯ：東レ社）の一方の表面に、酸化珪素系反射防止塗料（OA-201F：日産化学工業社）と実施例１で用いた樹脂層用塗布液を順次塗布し、乾燥、硬化させることにより、約１００ｎｍの酸化珪素系薄膜３と約４μｍの樹脂層２を形成し、図４の積層体１を製造した。
次いで、当該樹脂層２上に以下の組成の接着層用塗布液を塗布し、乾燥することにより約１０μｍの接着層６を形成して、当該接着層６を介して印刷物表面７に接着させた後（図５(ａ)）、ポリプロピレンフィルム５を剥離して、酸化珪素系薄膜３と樹脂層２とからなる積層体１を印刷物表面７に転写させた（図５(ｂ)）。

【００４１】
以上の実施例２のように剥離可能な支持体５に酸化珪素系薄膜３と樹脂層２とをこの順に積層する製造方法によって得られたものは、接着層６を介して印刷物表面７に積層体１を転写させることができ、印刷物表面７に長期間湿度や温度の影響を受けない反射防止処理を付与することができる。
【００４２】
【発明の効果】
本発明の積層体の製造方法によれば、塩基で中和されていないアニオン性高分子分散剤を用いて有機溶媒可溶型バインダー樹脂に微粒子を分散した樹脂層と酸化珪素系薄膜とを直接又は他の薄膜を介して積層することにより、このようにして得られた微粒子含有樹脂層と酸化珪素系薄膜とを積層した積層体は、長期において積層体としての所望の性能を持続できるという効果が得られる。
【図面の簡単な説明】
【図１】 本発明の積層体の製造方法によって得られる積層体の一例を示す示す断面図。
【図２】 本発明の積層体の製造方法によって得られる積層体の他の例を示す断面図。
【図３】 本発明の積層体の製造方法によって得られる積層体の他の例を示す断面図。
【図４】 本発明の積層体の製造方法によって得られる積層体の他の例を示す断面図。
【図５】 本発明の積層体の製造方法によって得られる積層体の利用形態を示す断面図。
【符号の説明】
１・・・積層体
２・・・樹脂層
３・・・酸化珪素系薄膜
４・・・他の薄膜
５・・・支持体
６・・・接着層
７・・・被着体[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a laminate of a resin layer in which fine particles are dispersed in an organic solvent-soluble binder resin and a silicon oxide thin film, and in particular, a laminate excellent in durability of a silicon oxide thin film laminated with a resin layer. The present invention relates to a method for manufacturing a body.
[0002]
[Prior art]
Conventionally, for example, there are antireflection films and antireflection film transfer films provided with a silicon oxide thin film having an optical film thickness of ¼ of the wavelength λ as an antireflection film.
[0003]
Since such an antireflection film is a thin film having an optical film thickness of about 0.1 μm, it is extremely difficult to have high hardness by itself, and generally wear resistance is obtained by laminating with a hard coat layer. Reinforced properties and scratch resistance.
[0004]
Therefore, as a hard coat layer serving as a base of such an antireflection film, an inorganic oxide fine particle or the like is used to increase the refractive index difference with the silicon oxide thin film that is an antireflection film as much as possible. There have been proposed hard coat layers in which high refractive index fine particles are dispersed in thermosetting resin or ionizing radiation curable resin to increase the refractive index (JP-A-3-68901, JP-A-8-179123). The present applicant has also proposed a print surface protective film (Japanese Patent Laid-Open No. 11-77874), a protective film transfer material (Japanese Patent Laid-Open No. 11-268166) and the like using such a hard coat layer.
[0005]
[Problems to be solved by the invention]
However, the laminate in which the fine particle-containing resin layer and the silicon oxide thin film are laminated in this way exhibits desired performance in the initial stage, but the silicon oxide thin film disappears when used over a long period of time. There was a problem that the initial performance was lost and the sustainability of the desired performance was poor.
[0006]
[Means for Solving the Problems]
Accordingly, the present inventor has continued intensive research to solve this problem, and uses natural fats and oils that are generally used as fine particle dispersants in organic solvent-soluble binder resins for such applications as raw materials. Attention was paid to the presence of anionic surfactant-type dispersants. As a result of further research, the inventor of the present invention uses a base such as an alkali metal ion in order to dissolve such a low molecular weight anionic surfactant type dispersant made from natural fats and oils in an organic solvent. The bases such as metal ions bleed out into the silicon oxide thin film and react with external moisture to generate alkali hydroxide, which dissolves and disappears the silicon oxide thin film. It came to the idea that it might be.
[0007]
Therefore, as a result of intensive studies on the dispersant for such applications, the present inventors have found that a high molecular weight dispersant can be dissolved in an organic solvent without being neutralized with a base. The present invention has been completed.
[0008]
That is, the method for producing a laminate of the present invention is a method for producing a laminate in which a resin layer in which fine particles are dispersed in an organic solvent-soluble binder resin and a silicon oxide thin film are laminated directly or via another thin film. a is, the dispersion into the binder resin of the fine particles, is characterized in that using an anionic polymer dispersant having an average molecular weight 2000-5000 that are not neutralized with a base.
[0009]
Moreover, the manufacturing method of the laminated body of this invention is characterized by laminating | stacking the said resin layer and a silicon oxide type thin film on this support surface in this order.
[0010]
Moreover, the manufacturing method of the laminated body of this invention is characterized by laminating | stacking a silicon oxide type thin film and the said resin layer in this order on the peelable support surface.
[0011]
In the method for producing a laminate of the present invention, the binder resin is made of an ionizing radiation curable resin or a thermosetting resin, and the resin layer is a hard coat layer.
[0012]
Moreover, the manufacturing method of the laminated body of this invention is characterized by microparticles | fine-particles consisting of high refractive index fine particles, and the said resin layer being a high refractive index layer.
[0013]
Moreover, the manufacturing method of the laminated body of this invention is a thing characterized by a silicon oxide type thin film and another thin film functioning as an antireflection layer.
[0014]
BEST MODE FOR CARRYING OUT THE INVENTION
The manufacturing method of the laminated body 1 of this invention is demonstrated in detail.
[0015]
In the method for producing the laminate 1 of the present invention, the resin layer 2 in which fine particles are dispersed in an organic solvent-soluble binder resin and the silicon oxide thin film 3 are directly (FIG. 1) or via another thin film 4 (FIG. 2). ) A method for laminating, wherein an anionic polymer dispersant not neutralized with a base is used for dispersing the fine particles in the binder resin.
[0016]
Therefore, in manufacturing the laminated body 1 in this way, it is desirable that there is a thing that becomes the support 5 for laminating the resin layer 2 and the silicon oxide thin film 3. The stacking order may be a method in which the resin layer 2 and the silicon oxide thin film 3 are stacked in this order (FIG. 3) on the surface of the support 5 depending on the form of use of the stack 1. A method of laminating the silicon oxide thin film 3 and the resin layer 2 in this order (FIG. 4) may be used. Therefore, when the stacking order with respect to the support 5 is the latter, as a use form of the stack 1, after being attached to another adherend 7 via the adhesive layer 6 or the like (FIG. 5A), By peeling off the support 5, the laminate 1 can be transferred to another adherend 7 (FIG. 5B) and used.
[0017]
Organic solvent-soluble binder resin for dispersing the fine particles of the present invention includes organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and other ketones, methyl cellosolve, ethers such as ethyl cellosolve, ethyl acetate, butyl acetate, It is not particularly limited as long as it is a resin that is soluble in an organic solvent such as esters such as cellosolve acetate, alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, and butyl alcohol, and aromatic hydrocarbons such as benzene, toluene, and xylene. Polyester resin, acrylic resin, polyester acrylate resin, polyurethane acrylate resin, epoxy acrylate resin, cellulose resin, acetal resin, vinyl resin, polyethylene resin, polystyrene resin, polyester resin Propylene resin, can be used polyamide resins, polyimide resins, melamine resins, phenol resins, silicone resins, thermoplastic resins such as fluorine-based resin, thermosetting resin, an ionizing radiation curing resin.
[0018]
In particular, in order to make the obtained resin layer 2 a hard coat layer, it is preferable to employ a resin whose crosslink density is improved by curing such as a thermosetting resin or an ionizing radiation curable resin.
[0019]
Examples of the thermosetting resin used herein include crosslinkable resins such as silicone, melamine, epoxy, aminoalkyd, urethane, acrylic, polyester, and phenol. These can be used alone, but it is preferable to add a curing agent in order to further improve the crosslinkability and the hardness of the crosslinked cured resin layer.
[0020]
As the ionizing radiation curable resin used here, a photopolymerizable prepolymer that can be crosslinked and cured by irradiation with ionizing radiation (ultraviolet rays or electron beams) can be used. An acrylic prepolymer having two or more acryloyl groups in one molecule and having a three-dimensional network structure by crosslinking and curing can be mentioned. As such an acrylic prepolymer, polyester acrylate, urethane acrylate, epoxy acrylate, melamine acrylate and the like can be used. This photopolymerizable prepolymer can be used alone, but a photopolymerizable monomer, a photopolymerizable initiator, an ultraviolet sensitizer, and the like are added in order to further improve the crosslink curability and the hardness of the crosslink cured resin layer. It is preferable.
[0021]
Here, as the photopolymerizable monomer, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, neopentyl glycol diacrylate, tripropylene glycol triacrylate, diethylene glycol diacrylate, A polyfunctional monomer such as 1,6-hexanediol diacrylate is exemplified. Examples of the photopolymerization initiator include acetophenone, benzophenone, Michler's ketone, benzoin, benzylmethyl ketal, benzoylbenzoate, α-acyloxime ester, thioxanthones, and the like, and examples of the ultraviolet sensitizer include n-butylamine, triethylamine. , Tri-n-butylphosphine and the like.
[0022]
The fine particles of the present invention are not particularly limited, but have a positively charged surface potential and are well dispersed in an organic solvent-soluble binder resin by an anionic polymer dispersant. Is preferred. Examples of such fine particles include metal oxide fine particles. In particular, in order to make the resin layer 2 a high refractive index layer, ZnO, TiO ₂ , SnO ₂ , ITO, ZrO ₂ , CeO ₂ , Sb _{2 are used.} High refractive index fine particles such as O ₅ , Bi ₂ O ₃ , ZnS, Y ₂ O ₃ , La ₂ O ₃ , Ta ₂ O ₅ are preferably used.
[0023]
The mixing ratio of the organic solvent-soluble binder resin and the fine particles as described above is not originally limited in the present invention, but in order to make the resin layer a hard coat layer and a high refractive index layer, an organic solvent is used. It is desirable that the fine particles be 100 to 1000 parts by weight, preferably 300 to 800 parts by weight with respect to 100 parts by weight of the soluble binder resin.
[0024]
Next, an anionic polymer dispersant that is not neutralized with a base used for dispersing fine particles in these organic solvent-soluble binder resins will be described.
[0025]
The anionic polymer dispersant of the present invention is used in the form of an acid not neutralized with a base such as an alkali metal, and is a homopolymer or copolymer having a functional group such as carboxylic acid, sulfonic acid or phosphonic acid. Terpolymer and the like. Examples of the monomer that gives such an acid functional group include acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, mesaconic acid, fumaric acid, citraconic acid, vinyl acetic acid, acrylicoxypropionic acid, Examples thereof include vinyl sulfonic acid, styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, allyl sulfonic acid, allyl phosphonic acid, and vinyl phosphonic acid.
[0026]
The anionic polymer dispersant can also be formed in part from monomers that do not contribute to functionality, such as carboxylic, sulfone or phosphonic acid of the polymer, and the functionality of carboxylic, sulfone or phosphonic acid of such polymer. Non-contributing monomers include, for example, methyl, ethyl, and butyl acrylate, and acrylic acid and methacrylic acid alkyl esters such as methyl, butyl, and isobutyl methacrylate, hydroxyethyl and hydroxypropyl acrylate, and acrylic acid such as methacrylate. And hydroxyalkyl esters of methacrylic acid, acrylamide, methacrylamide, Nt-butylacrylamide, N-methylacrylamide, N, N-dimethylacrylamide, dimethylaminoethyl acrylate DOO, dimethylaminoethyl methacrylate, N- vinylpyrrolidone, N- vinylformamide, phosphoethyl methacrylate, acrylonitrile, vinyl acetate, or styrene or the like.
[0027]
Such an anionic polymer dispersant has an average molecular weight of 2,000 to 5,000, and by increasing the molecular weight in this way, the nonpolar portion as a whole can be increased. It is thought that it becomes easy to solubilize in an organic solvent without neutralizing with a base.
[0028]
The addition ratio of the anionic polymer dispersant not neutralized with such a base to the fine particles is 1.0 to 10.0 mg, preferably 2.0 to 6.0 mg per 1 m ² of the surface area of the fine particles. It is desirable to be. By setting it within the range of 1.0 to 10.0 mg, the polymer dispersant is appropriately adsorbed on the entire surface of the fine particles and exhibits excellent dispersibility.
[0029]
The resin layer 2 of the present invention is prepared by appropriately mixing an anionic polymer dispersant not neutralized with a base and fine particles in a binder resin solution obtained by dissolving an organic solvent-soluble binder resin in an organic solvent. A fine particle dispersion resin solution is prepared by a machine to prepare a fine particle dispersed resin solution, and an organic solvent-soluble binder resin, an organic solvent, and other additives are further appropriately mixed with the fine particle dispersed resin solution to prepare a resin layer coating solution. And it can provide by apply | coating, drying, hardening | curing on the support body 5 or the silicon oxide type thin film 3, etc.
[0030]
Next, the silicon oxide thin film 3 of the present invention will be described. The silicon oxide thin film 3 of the present invention is provided with silicon oxide in the form of a thin film, and is applied to various applications. In particular, the outermost layer of a single-layer antireflection film or a multilayer antireflection film, etc. A typical example thereof is a film having a thickness that functions as an antireflection layer.
[0031]
As a film thickness that functions as such an antireflection film, an optical film thickness that is 1/4 of the wavelength with respect to a specific wavelength (a main wavelength for the purpose of antireflection) is provided. The optical film thickness referred to here is a film thickness obtained by the product nd of the refractive index n of the film and the mechanical film thickness d. Such an antireflection film is generally an extremely thin film having a thickness of several hundred nm or less, and is easily dissolved and disappeared by alkali. It is extremely important to prevent the bases such as from bleeding out.
[0032]
Further, in order to make such a silicon oxide thin film 3 function as an antireflection film with better performance, it is used as the outermost layer of the multilayer antireflection film as described above, and as such, It can be obtained by appropriately laminating one or more other thin films 4 such as a high refractive index thin film, a medium refractive index thin film, and a low refractive index thin film having an optical film thickness based on a specific wavelength on the silicon oxide thin film 3. In addition, the other thin film 4 is also a thin film of several hundred nm or less, and is not sufficient for preventing base bleed out from the resin layer 2 to the silicon oxide thin film 3. The purpose of making 2 free of bases such as alkali metal salts is not lost.
[0033]
The silicon oxide thin film 3 as described above can be obtained by providing a silicon oxide such as SiO ₂ by a vacuum film forming method such as a vacuum deposition method, a sputtering method or an ion plating method, or by hydrolyzing a silicon alkoxide. Examples thereof include those prepared by applying a silane antireflection coating such as an adjusted silicon oxide sol.
[0034]
【Example】
Examples of the present invention will be described below. “Part” and “%” are based on weight unless otherwise specified.
[0035]
[Example 1]
On one surface of a polyethylene terephthalate film 5 (Cosmo Shine A4100: Toyobo Co., Ltd.) having a thickness of 188 μm, a coating solution for the resin layer having the following composition was applied, dried at 90 ° C. for 2 minutes, and then irradiated with ultraviolet rays with a high-pressure mercury lamp for 1-2. A resin layer 2 having a dry coating thickness of about 4 μm is formed by second irradiation, and then a SiO ₂ film 3 (refractive index 1.46) is formed on the resin layer 2 to a thickness of about 95 nm by vacuum deposition. Thus, the laminate 1 of FIG. 3 was manufactured.

[0036]
[Comparative example]
A comparison was made in the same manner as in Example 1 except that an anionic surfactant type dispersant (sodium dioctyl sulfosuccinate <Lapisol B80: NOF Corporation>) was used instead of the anionic polymer dispersant used in Example 1. An example laminate was produced.
[0037]
The total light transmittance (JIS-K7105) of the laminates obtained by the production methods of Example 1 and Comparative Example above was measured before and after the moisture resistance accelerated test (90% RH, 60 ° C., 140 hours). The results are shown in Table 1.
[0038]
[Table 1]

[0039]
As is clear from Table 1, the laminate 1 of Example 1 shows almost no change in the total light transmittance before and after the accelerated humidity resistance test, and the antireflection effect which is a function of the silicon oxide thin film is impaired. However, in the laminate of the comparative example, the total light transmittance after the moisture resistance accelerated test was extremely lowered, the silicon oxide thin film disappeared, and the antireflection effect was lost.
[0040]
[Example 2]
On one surface of a polypropylene film 5 having a thickness of 60 μm (Treffan BO: Toray Industries, Inc.), a silicon oxide antireflection coating (OA-201F: Nissan Chemical Industries, Ltd.) and the coating solution for the resin layer used in Example 1 are sequentially applied. By applying, drying and curing, a silicon oxide thin film 3 having a thickness of about 100 nm and a resin layer 2 having a thickness of about 4 μm were formed, and the laminate 1 shown in FIG. 4 was manufactured.
Next, an adhesive layer coating solution having the following composition was applied onto the resin layer 2 and dried to form an adhesive layer 6 of about 10 μm, which was adhered to the printed surface 7 via the adhesive layer 6. Thereafter (FIG. 5A), the polypropylene film 5 was peeled off, and the laminate 1 composed of the silicon oxide thin film 3 and the resin layer 2 was transferred to the printed surface 7 (FIG. 5B).

[0041]
What was obtained by the manufacturing method of laminating the silicon oxide thin film 3 and the resin layer 2 in this order on the peelable support 5 as in Example 2 above was laminated on the printed surface 7 via the adhesive layer 6. The body 1 can be transferred, and an antireflection treatment that is not affected by humidity or temperature for a long period of time can be applied to the printed surface 7.
[0042]
【The invention's effect】
According to the method for producing a laminate of the present invention, a resin layer in which fine particles are dispersed in an organic solvent-soluble binder resin using an anionic polymer dispersant that is not neutralized with a base and a silicon oxide thin film are directly formed. Alternatively, the laminated body obtained by laminating the fine particle-containing resin layer and the silicon oxide thin film obtained by laminating through another thin film can maintain desired performance as a laminated body for a long time. Is obtained.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view showing an example of a laminate obtained by the laminate production method of the present invention.
FIG. 2 is a cross-sectional view showing another example of a laminate obtained by the method for producing a laminate of the present invention.
FIG. 3 is a cross-sectional view showing another example of a laminate obtained by the laminate production method of the present invention.
FIG. 4 is a cross-sectional view showing another example of a laminate obtained by the laminate production method of the present invention.
FIG. 5 is a cross-sectional view showing a utilization form of a laminate obtained by the laminate production method of the present invention.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 ... Laminated body 2 ... Resin layer 3 ... Silicon oxide type thin film 4 ... Other thin film 5 ... Support body 6 ... Adhesion layer 7 ... Adhering body

Claims (5)

A method for producing a laminate in which a resin layer in which fine particles are dispersed in an organic solvent-soluble binder resin and a silicon oxide thin film are laminated directly or via another thin film, wherein the fine particles are applied to the binder resin. A method for producing a laminate , wherein an anionic polymer dispersant having an average molecular weight of 2000 to 5000 which is not neutralized with a base is used for dispersion. The polymer dispersant is mixed with a fine particle surface area of 1 m. ² The method for producing a laminate according to claim 1, wherein 1.0 to 10.0 mg is added per unit.   The method for producing a laminate according to claim 1, wherein the resin layer and the silicon oxide thin film are laminated in this order on a support surface.   The method for producing a laminate according to claim 1, wherein the silicon oxide thin film and the resin layer are laminated in this order on a peelable support surface. The method for producing a laminate according to any one of claims 1 to 4, wherein the silicon oxide thin film is formed by a vacuum film forming method.

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