JP2011053455A - Glare-proof hard coat film - Google Patents
Glare-proof hard coat film Download PDFInfo
- Publication number
- JP2011053455A JP2011053455A JP2009202443A JP2009202443A JP2011053455A JP 2011053455 A JP2011053455 A JP 2011053455A JP 2009202443 A JP2009202443 A JP 2009202443A JP 2009202443 A JP2009202443 A JP 2009202443A JP 2011053455 A JP2011053455 A JP 2011053455A
- Authority
- JP
- Japan
- Prior art keywords
- hard coat
- mass
- coat layer
- parts
- glare
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000178 monomer Substances 0.000 claims abstract description 80
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 54
- 239000011737 fluorine Substances 0.000 claims abstract description 51
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000011248 coating agent Substances 0.000 claims abstract description 33
- 238000000576 coating method Methods 0.000 claims abstract description 33
- 239000010419 fine particle Substances 0.000 claims abstract description 31
- 239000000654 additive Substances 0.000 claims abstract description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000000996 additive effect Effects 0.000 claims abstract description 19
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 19
- 239000010703 silicon Substances 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims description 29
- 239000000758 substrate Substances 0.000 claims description 11
- -1 polydimethylsiloxane Polymers 0.000 claims description 8
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 7
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- 238000010186 staining Methods 0.000 abstract 2
- 239000012530 fluid Substances 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 15
- 239000007788 liquid Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 8
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 4
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 4
- 230000003373 anti-fouling effect Effects 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Natural products OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical group 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 230000004313 glare Effects 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 210000002374 sebum Anatomy 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Liquid Crystal (AREA)
- Laminated Bodies (AREA)
- Optical Elements Other Than Lenses (AREA)
Abstract
Description
本発明は、油性の汚れ及び水性の汚れの拭取り性並びに耐擦傷性に優れた防眩性ハードコートフィルムに関する。 The present invention relates to an antiglare hard coat film excellent in wiping properties of oily and aqueous stains and scratch resistance.
液晶ディスプレイ等の表示体の表面は様々な環境に晒されるため、非常に傷がつきやすい、或いは汚れやすい状況にある。通常、表示体の表面には、傷を付きにくくするため（ハードコート性を持たせるため）、若しくは傷を目立ち難くするため（防眩性を持たせるため）、防眩性ハードコートフィルムが用いられている（例えば、特許文献１を参照）。 Since the surface of a display body such as a liquid crystal display is exposed to various environments, it is very easily damaged or dirty. Usually, an antiglare hard coat film is used on the surface of the display body to make it hard to be scratched (in order to have hard coat properties) or to make the scratches inconspicuous (to give antiglare properties). (For example, see Patent Document 1).
この表示体の表面に付着した皮脂等の汚れは、水及び洗剤等の界面活性剤を染みこませた布等により拭取ることで除去しているが、水及び洗剤などによる汚れの除去は、汚れの種類によっては十分に拭取れないだけでなく、拭取れるまで何回も拭く操作を繰り返すために非常に煩わしいものとなっていた。 Dirt such as sebum adhering to the surface of the display body is removed by wiping with a cloth soaked with a surfactant such as water and detergent. Depending on the type of dirt, not only could it be wiped off sufficiently, but it was very troublesome to repeat the wiping operation several times until it was wiped off.
このような問題に対して、例えばフッ素系添加剤を用いる方法が知られている（例えば、特許文献２を参照）。 For such a problem, for example, a method using a fluorine-based additive is known (see, for example, Patent Document 2).
しかしながら、特許文献２に記載の防眩性ハードコートフィルムにおいては、油性（油性ペン）の汚れは拭取りやすいが、水性（水性ペン）の汚れは拭き取り難いという問題があった。 However, the antiglare hard coat film described in Patent Document 2 has a problem that oily (oil-based pen) dirt is easy to wipe off, but aqueous (aqueous pen) dirt is difficult to wipe off.
ところで、特許文献３に記載されているフッ素モノマー（特許文献３の例えば第７５頁、化９５）は、低屈折率を維持しながら、耐擦傷性、耐摩耗性が改善された反射防止膜を実現できるフッ素モノマーであると記載されているが、防汚性に優れるハードコート層へ用いることに関する記載はない。 By the way, the fluorine monomer described in Patent Document 3 (for example, page 75 of Chemical Document 3, page 95) is an antireflection film with improved scratch resistance and wear resistance while maintaining a low refractive index. Although it is described that it is a fluorine monomer that can be realized, there is no description about using it for a hard coat layer having excellent antifouling properties.
そこで、本発明の目的とするところは、油性（油性ペン）の汚れ及び水性（水性ペン）の汚れの拭取りやすさに優れると共に、耐擦傷性に優れる防眩性ハードコートフィルムを提供することにある。 Accordingly, an object of the present invention is to provide an antiglare hard coat film which is excellent in ease of wiping off oily (oil-based pen) dirt and aqueous (aqueous pen) dirt and is excellent in scratch resistance. It is in.
前記の目的を達成するために、第１の発明の防眩性ハードコートフィルムは、透明基材フィルム上に防眩性ハードコート層を積層した防眩性積層体であって、前記防眩性ハードコート層は、ａ）下記に示す化学式（１）のフッ素モノマーを０．２〜０．５質量部、ｂ）化学式（１）のフッ素モノマーと共重合可能なモノマーを６０〜９０質量部、ｃ）透光性有機微粒子を１０〜４０質量部及びｄ）シリコン系添加剤を０．１〜０．４質量部含有する防眩性ハードコート層用塗液の硬化物であることを特徴とする。
（但し、ｂ）化学式（１）のフッ素モノマーと共重合可能なモノマーと、ｃ）透光性有機微粒子の合計は１００質量部である。）
In order to achieve the above object, the antiglare hard coat film of the first invention is an antiglare laminate in which an antiglare hard coat layer is laminated on a transparent substrate film, wherein the antiglare property is The hard coat layer is a) 0.2 to 0.5 parts by mass of a fluorine monomer represented by the following chemical formula (1), b) 60 to 90 parts by mass of a monomer copolymerizable with the fluorine monomer of chemical formula (1), c) A cured product of a coating solution for an antiglare hard coat layer containing 10 to 40 parts by mass of translucent organic fine particles and d) 0.1 to 0.4 parts by mass of a silicon-based additive. To do.
(However, the total of b) the monomer copolymerizable with the fluorine monomer of the chemical formula (1), and c) the light-transmitting organic fine particles is 100 parts by mass. )
第２の発明の防眩性ハードコートフィルムは、第１の発明において、前記シリコン系添加剤が、ポリエーテル変性ポリジメチルシロキサンであることを特徴とする。
The antiglare hard coat film of the second invention is characterized in that, in the first invention, the silicon-based additive is polyether-modified polydimethylsiloxane.
本発明によれば、次のような効果を発揮することができる。
第１の発明の防眩性ハードコートフィルムでは、油性（油性ペン）の汚れ及び水性（水性ペン）の汚れの拭取りが良好となると共に、耐擦傷性も向上する。
According to the present invention, the following effects can be exhibited.
In the antiglare hard coat film of the first invention, oily (oil-based pen) dirt and aqueous (aqueous pen) dirt can be wiped off, and the scratch resistance is also improved.
第２の発明の防眩性ハードコートフィルムでは、第１の発明の効果に加えて、油性（油性ペン）の汚れ及び水性（水性ペン）の汚れの拭取りがより一層良好となる。 In the antiglare hard coat film of the second invention, in addition to the effects of the first invention, wiping of oily (oil-based pen) dirt and aqueous (aqueous pen) dirt is further improved.
以下、本発明を具体化した実施形態について詳細に説明する。
＜防眩性ハードコートフィルム＞
本実施形態の防眩性ハードコートフィルムは、透明基材フィルム上に防眩性ハードコート層が積層されて構成されている。前記防眩性ハードコート層は、ａ）下記に示す化学式（１）のフッ素モノマーを０．２〜０．５質量部、ｂ）化学式（１）のフッ素モノマーと共重合可能なモノマーを６０〜９０質量部、ｃ）透光性有機微粒子を１０〜４０質量部及びｄ）シリコン系添加剤を０．１〜０．４質量部含有する防眩性ハードコート層用塗液の硬化物である。
〔但し、ｂ）化学式（１）のフッ素モノマーと共重合可能なモノマーと、ｃ）透光性有機微粒子の合計は１００質量部である。〕
DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments embodying the present invention will be described in detail.
<Anti-glare hard coat film>
The antiglare hard coat film of this embodiment is constituted by laminating an antiglare hard coat layer on a transparent substrate film. The antiglare hard coat layer includes a) 0.2 to 0.5 parts by mass of a fluorine monomer represented by the following chemical formula (1), and b) 60 to 60 monomers copolymerizable with the fluorine monomer represented by the chemical formula (1). 90 parts by mass, c) 10 to 40 parts by mass of translucent organic fine particles, and d) a cured product of a coating solution for an antiglare hard coat layer containing 0.1 to 0.4 parts by mass of a silicon-based additive. .
[However, the total of b) the monomer copolymerizable with the fluorine monomer of the formula (1) and c) the translucent organic fine particles is 100 parts by mass. ]
次に、防眩性ハードコートフィルムの構成要素について順に説明する。
〔透明基材フィルム〕
透明基材フィルムは防眩性ハードコートフィルムの基材（ベース材）となるものであって、透明樹脂フィルム等が用いられ、特に制限されない。透明基材フィルムを形成する樹脂材料として具体的には、ポリ（メタ）アクリル系樹脂、トリアセテートセルロース（ＴＡＣ）系樹脂、ポリエチレンテレフタレート（ＰＥＴ）系樹脂、ポリカーボネート系樹脂等が挙げられる。それらの中でも、汎用性などの観点からトリアセテートセルロース（ＴＡＣ）系樹脂及びポリエチレンテレフタレート（ＰＥＴ）系樹脂が好ましい。
Next, components of the antiglare hard coat film will be described in order.
[Transparent substrate film]
The transparent substrate film serves as a substrate (base material) for the antiglare hard coat film, and a transparent resin film or the like is used and is not particularly limited. Specific examples of the resin material forming the transparent base film include poly (meth) acrylic resins, triacetate cellulose (TAC) resins, polyethylene terephthalate (PET) resins, polycarbonate resins, and the like. Among them, triacetate cellulose (TAC) resin and polyethylene terephthalate (PET) resin are preferable from the viewpoint of versatility.
透明基材フィルムの厚みは通常１０〜５０００μｍ、好ましくは２５〜１０００μｍ、さらに好ましくは３５〜５００μｍである。
〔防眩性ハードコート層〕
続いて、防眩性ハードコート層について説明する。防眩性ハードコート層はその表面に凹凸を有し、その凹凸に光が反射して拡散され（表面拡散性）、防眩性を発現することができる機能を備えている。さらに、油性（油性ペン）の汚れ及び水性（水性ペン）の汚れの拭取り性と防汚性の機能並びに耐擦傷性の機能を備えている。
The thickness of the transparent substrate film is usually 10 to 5000 μm, preferably 25 to 1000 μm, more preferably 35 to 500 μm.
[Anti-glare hard coat layer]
Next, the antiglare hard coat layer will be described. The antiglare hard coat layer has irregularities on its surface, and light is reflected and diffused on the irregularities (surface diffusibility), and has a function capable of exhibiting antiglare properties. Further, it has a function of wiping off oil-based (oil-based pen) dirt and water-based (water-based pen) dirt, an antifouling function, and a scratch resistance function.
該防眩性ハードコート層は、前述のように化学式（１）のフッ素モノマーと、化学式（１）のフッ素モノマーと共重合可能なモノマーと、シリコン系添加剤と、透光性有機微粒子とを少なくとも含有する防眩性ハードコート層用塗液を硬化させた硬化物により形成される。また、防眩性ハードコート層用塗液中には、通常希釈溶剤、光重合開始剤、或いはその他の成分が配合される。
（化学式（１）のフッ素モノマー）
化学式（１）のフッ素モノマーは、汚れの拭取り性機能、防汚性機能、耐擦傷性機能等を発現するためのものである。また、化学式（１）のフッ素モノマーは、特開２００９−９１３８号公報に記載の方法により製造することができる。そのような化学式（１）のフッ素モノマーとしては、ダイキン工業（株）製のＤＡＣ−ＨＰ、オプツールＤＡＣ等を入手して用いることができる。
As described above, the antiglare hard coat layer comprises a fluorine monomer of the chemical formula (1), a monomer copolymerizable with the fluorine monomer of the chemical formula (1), a silicon-based additive, and translucent organic fine particles. It is formed of a cured product obtained by curing at least an antiglare hard coat layer coating solution. The antiglare hard coat layer coating liquid usually contains a diluent solvent, a photopolymerization initiator, or other components.
(Fluorine monomer of chemical formula (1))
The fluorine monomer of the chemical formula (1) is for developing a dirt wiping function, an antifouling function, an abrasion resistance function, and the like. In addition, the fluorine monomer represented by the chemical formula (1) can be produced by the method described in JP-A-2009-9138. As such a fluorine monomer of the chemical formula (1), DAC-HP, Optool DAC, etc. manufactured by Daikin Industries, Ltd. can be obtained and used.
化学式（１）のフッ素モノマーの含有量は、前記ｂ）のモノマー及びｃ）の透光性有機微粒子の合計量１００質量部に対して０．２〜０．５質量部である。フッ素モノマーの含有量が０．２質量部より少ない場合には、フッ素モノマーの機能を十分に発揮することができず、油性（油性ペン）の汚れ、及び水性（水性ペン）の汚れの拭取り性が低下する。その一方、０．５質量部より多い場合には、化学式（１）のフッ素モノマーがｂ）のモノマーに比べて耐擦傷性に劣るため、防眩性ハードコート層表面の耐擦傷性が低下する。
（化学式（１）のフッ素モノマーと共重合可能なモノマー）
化学式（１）のフッ素モノマーと共重合可能なモノマーは、防眩性とハードコート性を発現するための防眩性ハードコート層用塗液の主成分であり、任意に用いることができる。そのような化学式（１）のフッ素モノマーと共重合可能なモノマーとしては、単官能単量体、多官能単量体、ビニル基や（メタ）アクリロイル基を有するオリゴマー及びビニル基や（メタ）アクリロイル基を有する重合体の中から１種又は２種以上が選択して用いられる。
The content of the fluorine monomer of the chemical formula (1) is 0.2 to 0.5 parts by mass with respect to 100 parts by mass of the total amount of the monomer b) and the translucent organic fine particles c). When the content of the fluorine monomer is less than 0.2 parts by mass, the function of the fluorine monomer cannot be sufficiently exerted, and oily (oil-based pen) dirt and aqueous (aqueous pen) dirt are wiped off. Sex is reduced. On the other hand, when the amount is more than 0.5 parts by mass, the fluorine monomer of the chemical formula (1) is inferior in scratch resistance compared with the monomer of b), and thus the scratch resistance on the surface of the antiglare hard coat layer is lowered. .
(Monomer copolymerizable with fluorine monomer of chemical formula (1))
The monomer copolymerizable with the fluorine monomer of the chemical formula (1) is a main component of the antiglare hard coat layer coating liquid for exhibiting antiglare properties and hard coat properties, and can be arbitrarily used. Monomers that can be copolymerized with the fluorine monomer represented by the chemical formula (1) include monofunctional monomers, polyfunctional monomers, oligomers having vinyl groups and (meth) acryloyl groups, vinyl groups, and (meth) acryloyl groups. One or two or more types of polymers having a group are selected and used.
単官能単量体として具体的には、（メタ）アクリル酸アルキルエステル、（メタ）アクリル酸（ポリ）エチレングリコール基含有（メタ）アクリル酸エステル、スチレン、フマル酸アルキルエステル、Ｎ−ビニル−２−ピロリドン等が好ましい。 Specific examples of the monofunctional monomer include (meth) acrylic acid alkyl ester, (meth) acrylic acid (poly) ethylene glycol group-containing (meth) acrylic acid ester, styrene, fumaric acid alkyl ester, and N-vinyl-2. -Pyrrolidone and the like are preferable.
多官能単量体としては、多価アルコールと（メタ）アクリル酸とのエステル化合物、ウレタン変性アクリレート等の（メタ）アクリロイル基を２個以上含む多官能重合性化合物等が挙げられる。多価アルコールとしては、例えばエチレングリコール、ポリエチレングリコール、ネオペンチルグリコール、２，２'−チオジエタノール、ペンタエリスリトール、ジペンタエリスリトール等の３価以上のアルコール等が挙げられる。 Examples of the polyfunctional monomer include ester compounds of polyhydric alcohol and (meth) acrylic acid, polyfunctional polymerizable compounds containing two or more (meth) acryloyl groups such as urethane-modified acrylate, and the like. Examples of the polyhydric alcohol include trivalent or higher alcohols such as ethylene glycol, polyethylene glycol, neopentyl glycol, 2,2′-thiodiethanol, pentaerythritol, and dipentaerythritol.
化学式（１）のフッ素モノマーと共重合可能なモノマーの含有量は、該モノマー及びｃ）の透光性有機微粒子の合計量１００質量部に対して６０〜９０質量部である。このｂ）のモノマーの含有量が６０質量部より少ない場合には、相対的に透光性有機微粒子の割合が過剰になって防眩性ハードコート層のヘイズ値が高くなり過ぎる。その一方、９０質量部より多い場合には、透光性有機微粒子の割合が不足し、透光性有機微粒子の機能が十分に発揮されず、防眩性ハードコート層の防眩性が悪化する。
（シリコン系添加剤）
前記シリコン系添加剤は、汚れの拭取り性機能、防汚性機能、耐擦傷性機能等を発現するためのものである。そのようなシリコン系添加剤としては、ポリエーテル変性ポリジメチルシロキサン等が挙げられる。ポリエーテル変性ポリジメチルシロキサンとして具体的には、ビックケミー・ジャパン（株）製のＢＹＫ３０６、ＢＹＫ３３０、ＢＹＫ３３１、ＢＹＫ３３３、ＢＹＫ３３７、ＢＹＫ３４１、ＢＹＫ３４４、ＢＹＫ３４５、ＢＹＫ３４６、ＢＹＫ３７８等が挙げられる。
The content of the monomer copolymerizable with the fluorine monomer of the chemical formula (1) is 60 to 90 parts by mass with respect to 100 parts by mass of the total amount of the monomer and the translucent organic fine particles of c). When the content of the monomer b) is less than 60 parts by mass, the ratio of the translucent organic fine particles is relatively excessive, and the haze value of the antiglare hard coat layer becomes too high. On the other hand, when the amount is more than 90 parts by mass, the ratio of the translucent organic fine particles is insufficient, the function of the translucent organic fine particles is not sufficiently exhibited, and the antiglare property of the antiglare hard coat layer is deteriorated. .
(Silicon additive)
The silicon-based additive is for developing a dirt wiping function, an antifouling function, an abrasion resistance function, and the like. Examples of such silicon-based additives include polyether-modified polydimethylsiloxane. Specific examples of the polyether-modified polydimethylsiloxane include BYK 306, BYK 330, BYK 331, BYK 333, BYK 337, BYK 341, BYK 344, BYK 345, BYK 346, BYK 378 and the like manufactured by Big Chemie Japan Co., Ltd.
シリコン系添加剤の含有量は、前記ｂ）のモノマー（バインダー）と前記ｃ）の透光性有機微粒子の合計量１００質量部に対して０．１〜０．４質量部である。シリコン系添加剤の含有量が０．１質量部より少ない場合には、シリコン系添加剤の機能を十分に発揮することができず、油性（油性ペン）の汚れ、及び水性（水性ペン）の汚れの拭取り性が低下する。その一方、０．４質量部より多い場合には、防眩性ハードコート層表面の耐擦傷性が低下する。
（透光性有機微粒子）
前記透光性有機微粒子は、防眩性ハードコート層における光拡散機能、表面の凹凸形成による防眩機能等を発現するためのものである。該透光性有機微粒子は、任意に用いることができる。そのような透光性有機微粒子としては、例えば塩化ビニル、（メタ）アクリル単量体、スチレン及びエチレンから選択される少なくとも１種の単量体を重合して得られる重合体などから形成される。その中でも、屈折率の調整が容易な点から（メタ）アクリル重合体（屈折率１．４９）、ポリスチレン重合体（屈折率１．５４）、さらに、両単量体の共重合組成を変化させることにより、両重合体の屈折率の間で屈折率を任意に調整することができる点でスチレン−（メタ）アクリル共重合体であることが好ましい。
The content of the silicon-based additive is 0.1 to 0.4 parts by mass with respect to 100 parts by mass of the total amount of the monomer (binder) of b) and the translucent organic fine particles of c). When the content of the silicon-based additive is less than 0.1 parts by mass, the function of the silicon-based additive cannot be fully exerted, and oily (oil-based pen) dirt and aqueous (aqueous pen) Dirt wiping performance is reduced. On the other hand, when it is more than 0.4 parts by mass, the scratch resistance of the antiglare hard coat layer surface is lowered.
(Translucent organic fine particles)
The translucent organic fine particles are for exhibiting a light diffusing function in the antiglare hard coat layer, an antiglare function by forming irregularities on the surface and the like. The translucent organic fine particles can be arbitrarily used. Such translucent organic fine particles are formed, for example, from a polymer obtained by polymerizing at least one monomer selected from vinyl chloride, (meth) acrylic monomer, styrene and ethylene. . Among them, the (meth) acrylic polymer (refractive index 1.49), polystyrene polymer (refractive index 1.54), and the copolymer composition of both monomers are changed from the viewpoint of easy adjustment of the refractive index. By this, it is preferable that it is a styrene- (meth) acryl copolymer at the point which can adjust a refractive index arbitrarily between the refractive indexes of both polymers.
透光性有機微粒子の平均粒子径は、その機能を十分に発揮させるために通常１〜６μｍ、好ましくは２〜５μｍである。この平均粒子径が１μｍ未満の場合、防眩性ハードコート層表面における防眩性が不十分となる。その一方、６μｍを超える場合、防眩性ハードコート層の膜厚が厚くなり、生産性が損なわれる。ここで、前記平均粒子径はコールターカウンター法により測定し、測定された分布を粒子数分布に換算し、得られた粒子数分布から算出される値である。なお、コールターカウンター法は、電気抵抗を利用した粒子径測定法であり、粒子が細孔を通過する際に生じる２電極間の電気抵抗の変化を測定して平均粒子径を測定する方法である。 The average particle diameter of the light-transmitting organic fine particles is usually 1 to 6 μm, preferably 2 to 5 μm, in order to sufficiently exhibit its function. When this average particle diameter is less than 1 μm, the antiglare property on the surface of the antiglare hard coat layer is insufficient. On the other hand, when exceeding 6 micrometers, the film thickness of an anti-glare hard-coat layer will become thick and productivity will be impaired. Here, the average particle diameter is a value calculated from a particle number distribution obtained by measuring the distribution by a Coulter counter method, converting the measured distribution into a particle number distribution. The Coulter counter method is a particle size measurement method using electric resistance, and is a method of measuring an average particle diameter by measuring a change in electric resistance between two electrodes that occurs when particles pass through pores. .
透光性有機微粒子の含有量は、前記ｂ）のモノマー及びｃ）の透光性有機微粒子の合計量１００質量部中に１０〜４０質量部、好ましくは２０〜３５質量部である。透光性有機微粒子の含有量が１０質量部より少ない場合には、透光性有機微粒子の機能を十分に発揮することができず、満足できる防眩性が得られなくなる。その一方、４０質量部より多い場合には、防眩性ハードコート層のヘイズ値が高くなり過ぎ、防眩性ハードコートフィルムをディスプレイ表面に設置した際、白化等が生じると共に、シンチレーション（面ぎら）が生じて画像鮮明性が低下する。
（希釈溶剤）
防眩性ハードコート層用塗液の調製に用いられる希釈溶剤は、主に防眩性ハードコート層用塗液を透明基材フィルム上に塗布するにあたり、防眩性ハードコート層用塗液の粘度を調整するために用いられ、非重合性のものであれば特に制限されない。希釈溶剤としては、例えばトルエン、キシレン、酢酸エチル、酢酸プロピル、酢酸ブチル、プロピレングリコールモノメチルエーテルアセテート、メチルアルコール、エチルアルコール、イソプロピルアルコール、ブチルアルコール、ジアセトンアルコール、メチルエチルケトン、メチルイソブチルケトン等が挙げられる。
（その他の成分）
防眩性ハードコート層用塗液には、その他の成分を配合することができる。その他の成分としては、金属酸化物、光増感剤、安定化剤、紫外線吸収剤、赤外線吸収剤、酸化防止剤等が用いられる。
〔防眩性ハードコート層の形成〕
まず、防眩性ハードコート層用塗液を透明基材フィルム上に塗布した後、活性エネルギー線を照射して硬化させることにより、透明基材フィルム上に防眩性ハードコート層が積層される。
The content of the translucent organic fine particles is 10 to 40 parts by mass, preferably 20 to 35 parts by mass in 100 parts by mass of the total amount of the monomer b) and the translucent organic fine particles c). When the content of the light-transmitting organic fine particles is less than 10 parts by mass, the function of the light-transmitting organic fine particles cannot be sufficiently exhibited, and satisfactory antiglare properties cannot be obtained. On the other hand, when the amount is more than 40 parts by mass, the haze value of the antiglare hard coat layer becomes too high, and when the antiglare hard coat film is placed on the display surface, whitening occurs and scintillation (glare) ) Occurs and the image sharpness decreases.
(Diluted solvent)
The dilution solvent used for the preparation of the coating solution for the antiglare hard coat layer is mainly used for coating the coating solution for the antiglare hard coat layer on the transparent substrate film. It is used for adjusting the viscosity and is not particularly limited as long as it is non-polymerizable. Examples of the diluent solvent include toluene, xylene, ethyl acetate, propyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, diacetone alcohol, methyl ethyl ketone, and methyl isobutyl ketone. .
(Other ingredients)
Other components can be blended in the coating solution for the antiglare hard coat layer. Examples of other components include metal oxides, photosensitizers, stabilizers, ultraviolet absorbers, infrared absorbers, and antioxidants.
[Formation of antiglare hard coat layer]
First, after applying the antiglare hard coat layer coating liquid on the transparent base film, the anti-glare hard coat layer is laminated on the transparent base film by irradiating and curing the active energy ray. .
上記防眩性ハードコート層用塗液の塗布方法は特に制限されず、通常行なわれている塗布方法、例えばロールコート法、スピンコート法、ディップコート法、スプレーコート法、バーコート法、ナイフコート法、ダイコート法、インクジェット法、グラビアコート法等公知のいかなる方法も採用される。塗布に際しては、密着性を向上させるために、予め透明基材フィルム表面にコロナ放電処理等の前処理を施すことができる。 The application method of the antiglare hard coat layer coating liquid is not particularly limited, and is usually performed by, for example, roll coating, spin coating, dip coating, spray coating, bar coating, knife coating. Any known method such as a method, a die coating method, an ink jet method, or a gravure coating method may be employed. In application, in order to improve adhesion, pretreatment such as corona discharge treatment can be applied to the surface of the transparent substrate film in advance.
活性エネルギー線の照射に用いられる活性エネルギー線源としては、例えば高圧水銀ランプ、ハロゲンランプ、キセノンランプ、窒素レーザ、電子線加速装置、放射性元素等の線源等が使用される。この場合、活性エネルギー線の照射量は、紫外線の波長３６５ｎｍでの積算光量として５０〜５０００ｍＪ／ｃｍ２であることが好ましい。照射量が５０ｍＪ／ｃｍ２未満のときには、防眩性ハードコート層用塗液の硬化が不十分となるため好ましくない。一方、５０００ｍＪ／ｃｍ２を超えるときには、前記ａ）のフッ素モノマー、ｂ）のモノマー等の活性エネルギー線硬化型樹脂が着色する傾向を示すため好ましくない。 As an active energy ray source used for irradiation of active energy rays, for example, a high pressure mercury lamp, a halogen lamp, a xenon lamp, a nitrogen laser, an electron beam accelerator, a radioactive element or the like is used. In this case, it is preferable that the irradiation amount of an active energy ray is 50-5000 mJ / cm < 2 > as an integrated light quantity in ultraviolet wavelength 365nm. When the irradiation amount is less than 50 mJ / cm 2 , the curing of the antiglare hard coat layer coating solution becomes insufficient, such being undesirable. On the other hand, when it exceeds 5000 mJ / cm 2 , the active energy ray-curable resin such as the fluorine monomer of a) or the monomer of b) tends to be colored, which is not preferable.
以下に、製造例、実施例及び比較例を挙げて前記実施形態をさらに具体的に説明する。ここで、実施例１〜３の防眩性ハードコートフィルムは、透明基材フィルムの一方の面に防眩性ハードコート層が積層された構成のものである。また、各例における蒸留水接触角、ヘキサデカン接触角、油性ペン拭取り性、水性ペン拭取り性、ヘイズ値及び耐擦傷性については、下記に示す方法により測定した。
（１）蒸留水接触角
自動接触角計〔協和界面科学（株）製、型名 ＤＭ５００〕を用いて蒸留水接触角を測定した。
（２）ヘキサデカン接触角
自動接触角計〔協和界面科学（株）製、型名 ＤＭ５００〕を用いてヘキサデカン接触角を測定した。
（３）油性ペン拭取り性
油性ペンにゼブラ（株）製マッキーを用い、５ｃｍ内に重ならないよう連続して円を描く。その後、日本製紙クレシア（株）製キムワイプを用い、１００ｇ荷重にて５往復拭取りを実施した後、表面の跡を目視で観察し下記の３段階で評価した。
Hereinafter, the embodiment will be described more specifically with reference to production examples, examples, and comparative examples. Here, the anti-glare hard coat films of Examples 1 to 3 have a configuration in which an anti-glare hard coat layer is laminated on one surface of the transparent substrate film. Moreover, the distilled water contact angle, hexadecane contact angle, oil-based pen wiping property, aqueous pen wiping property, haze value and scratch resistance in each example were measured by the methods shown below.
(1) Distilled water contact angle Distilled water contact angle was measured using an automatic contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., model name: DM500).
(2) Hexadecane contact angle The hexadecane contact angle was measured using an automatic contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., model name: DM500).
(3) Oil-based pen wiping property Use a zebra-made Mackey on an oil-based pen and draw a circle continuously so as not to overlap within 5 cm. Then, after performing 5 reciprocal wipings with a load of 100 g using a Nippon Paper Crecia Co., Ltd. Kimwipe, the surface trace was visually observed and evaluated in the following three stages.
◎：油性ペンの跡が完全に無い場合
○：油性ペンの跡が一部残る場合
×：油性ペンの跡が残る場合
（４）水性ペン拭取り性
水性ペンに三菱鉛筆（株）製ＰＲＯＰＵＳを用い、５ｃｍ内に重ならないよう連続して円を描く。その後、日本製紙クレシア（株）製キムワイプを用い、１００ｇ荷重にて５往復拭取りを実施した後、表面の跡を目視で観察し下記の３段階で評価した。
◎: When there is no trace of oil-based pen ○: When trace of oil-based pen remains x: When trace of oil-based pen remains (4) Aqueous pen wiping property PROPUS manufactured by Mitsubishi Pencil Co., Ltd. is applied to the aqueous pen. Use a continuous circle so that it does not overlap within 5 cm. Then, after performing 5 reciprocal wipings with a load of 100 g using a Nippon Paper Crecia Co., Ltd. Kimwipe, the surface trace was visually observed and evaluated in the following three stages.
◎：水性ペンの跡が完全に無い場合
○：水性ペンの跡が一部残る場合
×：水性ペンの跡が残る場合
（５）ヘイズ値
ヘイズメーター〔日本電色工業（株）製、ＮＤＨ２０００〕を使用し、光学特性としてのヘイズ値を測定した。
（６）耐擦傷性
（株）本光製作所製消しゴム摩耗試験機の先端に、＃００００のスチールウールを固定し、２．５Ｎ（２５０ｇｆ）の荷重をかけて、被擦傷体であるフィルムの表面を１０往復摩擦した後の表面の傷を目視で観察し、下記の４段階で評価した。
◎: When there is no trace of aqueous pen ○: When some trace of aqueous pen remains x: When trace of aqueous pen remains (5) Haze value Haze meter [Nippon Denshoku Industries Co., Ltd., NDH2000] Was used to measure the haze value as an optical property.
(6) Scratch resistance The surface of the film, which is a scratched body, is fixed by attaching # 0000 steel wool to the tip of an eraser abrasion tester manufactured by Honko Seisakusho Co., Ltd. and applying a load of 2.5 N (250 gf). The surface scratches after 10 reciprocating rubs were visually observed and evaluated in the following 4 stages.
◎：ほぼ傷なし
○：傷５〜１５本
△：傷１５〜３０本
×：傷３１本以上
〔製造例１、防眩性ハードコート層用塗液（ＨＣ−１）の調製〕
化学式（１）のフッ素モノマーと共重合可能なモノマーとしてウレタンアクリレート〔１分子中にアクリロイル基を６個有するウレタンアクリレート（６官能ウレタンアクリレート）、分子量１４００、日本合成化学工業（株）製、紫光ＵＶ７６００Ｂ〕６８質量部、光重合開始剤として１−［４−（２−ヒドロキシエトキシ）フェニル］−２−ヒドロキシ−２−メチル−１−プロパン−１−オン〔チバ・スペシャルティ・ケミカルズ（株）製、イルガキュア（Ｉｒｇ.）２９５９〕３質量部、メチルイソブチルケトン（ＭＩＢＫ）９７質量部、透光性有機微粒子としてスチレン−アクリル共重合体の微粒子〔積水化成品（株）製、ＸＸ−２４Ｖ、平均粒子径は５．５μｍ、屈折率は１．５１〕３２質量部、及びフッ素モノマー〔ダイキン工業（株）製、オプツールＤＡＣ−ＨＰ、固形分換算、化学式（１）ｎ＝１６、Ｘ＝Ｆ〕０．２質量部、シリコン系添加剤〔ポリエーテル変性ジメチルポリシロキサン、ビック・ケミー（株）製、ＢＹＫ３０６〕０．２質量部を混合して防眩性ハードコート層用塗液（ＨＣ−１）を調製した。
（実施例１）
防眩性ハードコート層用塗液（ＨＣ−１）を、透明基材フィルムとして厚み１００μｍのポリエチレンテレフタレート（ＰＥＴ）フィルム上にロールコーターにて塗布し、８０℃で２分間乾燥した。その後、１２０Ｗ高圧水銀灯〔日本電池（株）製〕により紫外線を照射し（積算光量４００ｍＪ／ｃｍ２）、硬化させて防眩性ハードコートフィルムを作製した。防眩性ハードコート層の厚みは８．５μｍであった。
（実施例２）
防眩性ハードコート層用塗液（ＨＣ−１）の透光性有機微粒子を、スチレン−アクリル共重合体の微粒子〔積水化成品（株）製、ＳＳＸ−１０５ＴＮＤ、平均粒子径は５．０μｍ、屈折率は１．５０〕に、フッ素モノマーを化学式（１）（ｎ＝２、Ｘ＝Ｆ）０．３質量部に、シリコン系添加剤としてポリエーテル変性ジメチルポリシロキサン〔ビック・ケミー（株）製、ＢＹＫ３７８〕を用い、その含有量を０．１質量部とした防眩性ハードコート層用塗液（ＨＣ−２）に変更した以外は、実施例１と同様の条件で防眩性ハードコートフィルムを作製した。防眩性ハードコート層の厚みは８．４μｍであった。
（実施例３）
防眩性ハードコート層用塗液（ＨＣ−１）中の化学式（１）のフッ素モノマーと共重合可能なモノマーとしてジペンタエリスリトールヘキサアクリレート〔日本化薬（株）製、ＫＡＹＡＲＡＤ ＤＰＨＡ〕を用い、その含有量を７７質量部、透光性有機微粒子の含有量を２３質量部、フッ素モノマーの含有量を０．５質量部、シリコン系添加剤の含有量を０．４質量部とした防眩性ハードコート層用塗液（ＨＣ−３）に変更した以外は、全て実施例１と同様の条件で防眩性ハードコートフィルムを作製した。防眩性ハードコート層の厚みは８．５μｍであった。
（比較例１）
防眩性ハードコート層用塗液（ＨＣ−１）中のフッ素モノマーの含有量を０．４質量部とし、シリコン系添加剤として前記ポリエーテル変性ジメチルポリシロキサン〔ビック・ケミー（株）製、ＢＹＫ３７８〕を用い、その含有量を０．０５質量部に変更して防眩性ハードコート層形成用塗液（ＨＣ−４）を調製した以外は、全て実施例１と同様の条件で防眩性ハードコートフィルムを作製した。防眩性ハードコート層の厚みは８．７μｍであった。
（比較例２）
防眩性ハードコート層用塗液（ＨＣ−１）中の化学式（１）のフッ素モノマーと共重合可能なモノマーの含有量を７４質量部、透光性有機微粒子の含有量を２６質量部、フッ素モノマーの含有量を０．０質量部、シリコン系添加剤の含有量を０．５質量部に変更して防眩性ハードコート層用塗液（ＨＣ−５）を調製した以外は、全て実施例１と同様の条件で防眩性ハードコートフィルムを作製した。防眩性ハードコート層の厚みは８．５μｍであった。
（比較例３）
防眩性ハードコート層用塗液（ＨＣ−１）中の化学式（１）のフッ素モノマーと共重合可能なモノマーとして前記ジペンタエリスリトールヘキサアクリレート〔日本化薬（株）製、ＫＡＹＡＲＡＤ ＤＰＨＡ〕を用い、その含有量を６４質量部、透光性有機微粒子の含有量を３６質量部、フッ素モノマーの含有量を０．１質量部、シリコン系添加剤の含有量を０．２質量部に変更して防眩性ハードコート層用塗液（ＨＣ−６）を調製した以外は、全て実施例１と同様の条件で防眩性ハードコートフィルムを作製した。
（比較例４）
防眩性ハードコート層用塗液（ＨＣ−６）中のフッ素モノマーの含有量を１．０質量部に変更して防眩性ハードコート層用塗液（ＨＣ−７）を調製した以外は、全て実施例１と同様の条件で防眩性ハードコートフィルムを作製した。
（比較例５）
防眩性ハードコート層用塗液（ＨＣ−１）中のフッ素モノマーとして、化学式（１）のフッ素モノマー以外のフッ素モノマー〔チバ・ジャパン（株）製、ＥＦＫＡ３６００〕を使用した以外は、全て実施例１と同様の条件で防眩性ハードコートフィルムを作製した。
◎: Almost no scratch ○: 5-15 scratches Δ: 15-30 scratches ×: 31 or more scratches [Production Example 1, preparation of antiglare hard coat layer coating liquid (HC-1)]
Urethane acrylate as a monomer copolymerizable with the fluorine monomer of the chemical formula (1) [urethane acrylate having 6 acryloyl groups in one molecule (hexafunctional urethane acrylate), molecular weight 1400, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., purple light UV7600B ] 68 parts by mass, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one [manufactured by Ciba Specialty Chemicals Co., Ltd.] Irgacure (Irg.) 2959] 3 parts by mass, 97 parts by mass of methyl isobutyl ketone (MIBK), fine particles of styrene-acrylic copolymer as translucent organic fine particles [XX-24V, average particle by Sekisui Plastics Co., Ltd.] Diameter is 5.5 μm, refractive index is 1.51] 32 parts by mass, and fluorine monomer [Daikin Industries Co., Ltd., OPTOOL DAC-HP, solid content conversion, chemical formula (1) n = 16, X = F] 0.2 parts by mass, silicon-based additive [polyether-modified dimethylpolysiloxane, manufactured by Big Chemie Co., Ltd. BYK306] 0.2 parts by mass was mixed to prepare an antiglare hard coat layer coating solution (HC-1).
Example 1
The antiglare hard coat layer coating solution (HC-1) was applied as a transparent substrate film on a polyethylene terephthalate (PET) film having a thickness of 100 μm with a roll coater and dried at 80 ° C. for 2 minutes. Then, ultraviolet rays were irradiated with a 120 W high-pressure mercury lamp (manufactured by Nippon Battery Co., Ltd.) (integrated light amount 400 mJ / cm 2 ) and cured to produce an antiglare hard coat film. The thickness of the antiglare hard coat layer was 8.5 μm.
(Example 2)
Translucent organic fine particles of the antiglare hard coat layer coating liquid (HC-1) are converted into styrene-acrylic copolymer fine particles [SSX-105TND, manufactured by Sekisui Plastics Co., Ltd., average particle size is 5.0 μm. , Refractive index is 1.50], fluorine monomer is 0.3 parts by mass of chemical formula (1) (n = 2, X = F), and polyether-modified dimethylpolysiloxane [BIC Chemie Co., Ltd.] as a silicon-based additive. ), BYK378], and the antiglare property was the same as in Example 1 except that the content was changed to the antiglare hard coat layer coating solution (HC-2) having a content of 0.1 parts by mass. A hard coat film was produced. The thickness of the antiglare hard coat layer was 8.4 μm.
(Example 3)
Using dipentaerythritol hexaacrylate [manufactured by Nippon Kayaku Co., Ltd., KAYARAD DPHA] as a monomer copolymerizable with the fluorine monomer of the chemical formula (1) in the antiglare hard coat layer coating liquid (HC-1), Antiglare with 77 parts by mass, 23 parts by mass of translucent organic fine particles, 0.5 parts by mass of fluorine monomer, and 0.4 parts by mass of silicon additive An antiglare hard coat film was produced under the same conditions as in Example 1 except that the coating liquid was changed to the coating liquid for the hard hard coat layer (HC-3). The thickness of the antiglare hard coat layer was 8.5 μm.
(Comparative Example 1)
The content of the fluorine monomer in the antiglare hard coat layer coating liquid (HC-1) is 0.4 parts by mass, and the polyether-modified dimethylpolysiloxane [manufactured by Big Chemie Co., Ltd. BYK378], and the antiglare hard coat layer forming coating solution (HC-4) was prepared by changing the content thereof to 0.05 parts by mass, and the same antiglare conditions as in Example 1. A hard coat film was produced. The thickness of the antiglare hard coat layer was 8.7 μm.
(Comparative Example 2)
The content of the monomer copolymerizable with the fluorine monomer of the chemical formula (1) in the antiglare hard coat layer coating liquid (HC-1) is 74 parts by mass, the content of the translucent organic fine particles is 26 parts by mass, All except that the content of the fluorine monomer was changed to 0.0 parts by mass and the content of the silicon-based additive was changed to 0.5 parts by mass to prepare an anti-glare hard coat layer coating solution (HC-5). An antiglare hard coat film was produced under the same conditions as in Example 1. The thickness of the antiglare hard coat layer was 8.5 μm.
(Comparative Example 3)
The dipentaerythritol hexaacrylate [manufactured by Nippon Kayaku Co., Ltd., KAYARAD DPHA] is used as a monomer copolymerizable with the fluorine monomer of the chemical formula (1) in the antiglare hard coat layer coating liquid (HC-1). The content was changed to 64 parts by mass, the translucent organic fine particle content to 36 parts by mass, the fluorine monomer content to 0.1 parts by mass, and the silicon additive content to 0.2 parts by mass. The antiglare hard coat film was prepared under the same conditions as in Example 1 except that the antiglare hard coat layer coating solution (HC-6) was prepared.
(Comparative Example 4)
The antiglare hard coat layer coating solution (HC-7) was prepared by changing the fluorine monomer content in the antiglare hard coat layer coating solution (HC-6) to 1.0 part by mass. All were produced under the same conditions as in Example 1 to produce an antiglare hard coat film.
(Comparative Example 5)
Except for using fluorine monomer other than the fluorine monomer of chemical formula (1) [EFKA3600, manufactured by Ciba Japan Co., Ltd.] as the fluorine monomer in the antiglare hard coat layer coating liquid (HC-1). An antiglare hard coat film was produced under the same conditions as in Example 1.
以上のようにして得られた防眩性ハードコートフィルムについて、蒸留水接触角、ヘキサデカン接触角、油性ペン拭取り性、水性ペン拭取り性、ヘイズ値及び耐擦傷性を前述の方法により測定し、それらの結果を表１に示した。 About the antiglare hard coat film obtained as described above, distilled water contact angle, hexadecane contact angle, oil pen wiping property, aqueous pen wiping property, haze value and scratch resistance were measured by the above-mentioned methods. The results are shown in Table 1.
その一方、比較例１においては、シリコン系添加剤の含有量が少ないことから、油性（油性ペン）の汚れ、及び水性（水性ペン）の汚れの拭取りが悪い結果であった。比較例２においては、フッ素モノマーを含有しないことから、水性（水性ペン）の汚れの拭取りが悪い結果であったことに加え、耐擦傷性に劣る結果となった。比較例３においては、フッ素系モノマーの含有量が少ないことから、水性（水性ペン）の汚れの付拭取り性が悪い結果であった。比較例４においては、フッ素モノマーの含有量が多いことから、耐擦傷性に劣る結果となった。比較例５においては、フッ素モノマーとして化学式（１）のフッ素モノマー以外のフッ素モノマーを用いたことから、油性ペン拭取り性及び水性ペン拭取り性が共に悪化した。 On the other hand, in Comparative Example 1, since the content of the silicon-based additive was small, the oily (oil-based pen) stain and the aqueous (aqueous pen) stain were poor. In Comparative Example 2, since no fluorine monomer was contained, the result of poor wiping off of water-based (aqueous pen) dirt was in addition to the result of poor scratch resistance. In Comparative Example 3, since the content of the fluorine-based monomer was small, the result of poor wiping of water-based (aqueous pen) stains was obtained. In Comparative Example 4, since the content of the fluorine monomer was large, the scratch resistance was inferior. In Comparative Example 5, since a fluorine monomer other than the fluorine monomer of the chemical formula (1) was used as the fluorine monomer, both the oil-based pen wiping property and the aqueous pen wiping property were deteriorated.
Claims (2)
〔但し、ｂ）化学式（１）のフッ素モノマーと共重合可能なモノマーと、ｃ）透光性有機微粒子の合計は１００質量部である。〕
[However, the total of b) the monomer copolymerizable with the fluorine monomer of the formula (1) and c) the translucent organic fine particles is 100 parts by mass. ]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009202443A JP5515525B2 (en) | 2009-09-02 | 2009-09-02 | Anti-glare hard coat film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009202443A JP5515525B2 (en) | 2009-09-02 | 2009-09-02 | Anti-glare hard coat film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2011053455A true JP2011053455A (en) | 2011-03-17 |
| JP5515525B2 JP5515525B2 (en) | 2014-06-11 |
Family
ID=43942512
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2009202443A Active JP5515525B2 (en) | 2009-09-02 | 2009-09-02 | Anti-glare hard coat film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5515525B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016163478A1 (en) * | 2015-04-07 | 2016-10-13 | 日産化学工業株式会社 | Curable composition for use in antiglare coating |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008029946A1 (en) * | 2006-09-08 | 2008-03-13 | Dai Nippon Printing Co., Ltd. | Contamination evaluation method, contamination evaluating device, optical member fabricating method, optical multilayer body, and display product |
| JP2009075354A (en) * | 2007-09-20 | 2009-04-09 | Dainippon Printing Co Ltd | Optical laminate, polarizing plate, and image display |
| JP2010244016A (en) * | 2009-03-18 | 2010-10-28 | Toppan Printing Co Ltd | Anti-glare film, polarizing plate and transmission type liquid crystal display |
| JP2010271424A (en) * | 2009-05-19 | 2010-12-02 | Sony Corp | Anti-glare film and method for manufacturing the same, and display device |
-
2009
- 2009-09-02 JP JP2009202443A patent/JP5515525B2/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008029946A1 (en) * | 2006-09-08 | 2008-03-13 | Dai Nippon Printing Co., Ltd. | Contamination evaluation method, contamination evaluating device, optical member fabricating method, optical multilayer body, and display product |
| JP2009075354A (en) * | 2007-09-20 | 2009-04-09 | Dainippon Printing Co Ltd | Optical laminate, polarizing plate, and image display |
| JP2010244016A (en) * | 2009-03-18 | 2010-10-28 | Toppan Printing Co Ltd | Anti-glare film, polarizing plate and transmission type liquid crystal display |
| JP2010271424A (en) * | 2009-05-19 | 2010-12-02 | Sony Corp | Anti-glare film and method for manufacturing the same, and display device |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016163478A1 (en) * | 2015-04-07 | 2016-10-13 | 日産化学工業株式会社 | Curable composition for use in antiglare coating |
| KR20170134577A (en) * | 2015-04-07 | 2017-12-06 | 닛산 가가쿠 고교 가부시키 가이샤 | Curable composition for repellent coating |
| JPWO2016163478A1 (en) * | 2015-04-07 | 2018-02-01 | 日産化学工業株式会社 | Curable composition for antiglare coating |
| KR102345843B1 (en) | 2015-04-07 | 2021-12-31 | 닛산 가가쿠 가부시키가이샤 | Curable composition for anti-glare coating |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5515525B2 (en) | 2014-06-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101870473B1 (en) | Anti-reflective film, anti-reflective film production method, polarization plate and image display device | |
| JP5560536B2 (en) | Hard coat layer composition and hard coat film | |
| JP6336804B2 (en) | Antireflection film, polarizing plate, cover glass, image display device, method for producing antireflection film, kit including antireflection film and cleaning cloth, and method for cleaning antireflection film | |
| TWI586534B (en) | Resin film, composition for resin film, and method of manufacturing the resin film | |
| CN104216032B (en) | Anti-dazzle hardness film coating | |
| TWI488747B (en) | Optical laminates and optical laminates | |
| CN104216033B (en) | Anti-dazzle hardness film coating | |
| JP2008197320A (en) | Antiglare coating composition, antiglare film, and method for manufacturing the same | |
| KR20140006922A (en) | Antireflection film, polarizing plate, and image display device | |
| JP5455146B2 (en) | Optical film | |
| KR101664735B1 (en) | Anti-fingerprint hardcoating composition and anti-fingerprint hardcoating film using the same | |
| JP2016122140A (en) | Anti-glare anti-reflection film and image display device using the same | |
| JP4887608B2 (en) | HARD COAT FILM AND DISPLAY DEVICE PROVIDED WITH THE FILM | |
| JP4860952B2 (en) | Coating composition for surface protective layer and antireflection film using the same | |
| JP2011076002A (en) | Transparent hard coat film | |
| JP2019055555A (en) | Active energy ray curable resin composition, laminate, method for manufacturing the same, and article | |
| JP5651921B2 (en) | Composition for hard coat layer | |
| JP2019168633A (en) | Resin composition for fingerprint fitting low refractive index layer and anti-reflection film | |
| JP5429150B2 (en) | Water repellent film | |
| JP2006348171A (en) | Curable resin composition for low refractive index coating, antireflection film | |
| JP2010186020A (en) | Antiglare antireflection film | |
| JP5515525B2 (en) | Anti-glare hard coat film | |
| JP6518374B2 (en) | Active energy ray curable resin composition, laminate, method for producing the same, and article | |
| JP2012068398A (en) | Hard-coated film | |
| JP6965582B2 (en) | A hard coat film, a touch panel provided with the hard coat film, and an image display device provided with the touch panel. |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20120704 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20130508 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20131112 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20140106 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20140304 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20140317 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5515525 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313113 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |