JP2016001217A5 - Base material with antireflection film and method for producing base material with antireflection film - Google Patents

Base material with antireflection film and method for producing base material with antireflection film Download PDF

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JP2016001217A5
JP2016001217A5 JP2014120437A JP2014120437A JP2016001217A5 JP 2016001217 A5 JP2016001217 A5 JP 2016001217A5 JP 2014120437 A JP2014120437 A JP 2014120437A JP 2014120437 A JP2014120437 A JP 2014120437A JP 2016001217 A5 JP2016001217 A5 JP 2016001217A5
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antireflection film
silica
film
base material
fine particles
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Priority to KR1020167026821A priority patent/KR102379944B1/en
Priority to PCT/JP2015/059981 priority patent/WO2015152171A1/en
Priority to CN201580017788.XA priority patent/CN106164190B/en
Priority to TW104110415A priority patent/TWI670335B/en
Publication of JP2016001217A publication Critical patent/JP2016001217A/en
Publication of JP2016001217A5 publication Critical patent/JP2016001217A5/en
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Claims (21)

基材上にハードコート膜および反射防止膜が形成されてなる反射防止膜付基材であって、
前記ハードコート膜が、平均粒子径が5〜300nmの表面処理金属酸化物微粒子(P)とマトリックス成分(MH)とからなり、
(i)前記表面処理金属酸化物微粒子(P)の前記ハードコート膜中の含有量(WPH)が50〜90重量%
(ii)前記マトリックス成分(MH)の前記ハードコート膜中の含有量(WRH)が10〜50重量%
(iii)前記含有量(WRH)と前記含有量(WPH)との比(W RH /W PH が0.12〜1.0
(iv)前記ハードコート膜の平均膜厚(TH)が1〜100μmであり
前記反射防止膜がシリカ系中空微粒子(A)とマトリックス成分(ML)とを含み
(a)前記シリカ系中空微粒子(A)の前記反射防止膜中の含有量(WPLA)が5〜80重量%
(b)前記マトリックス成分(ML)の前記反射防止膜中の含有量(WML)が20〜95重量%
(c)前記反射防止膜の膜厚(TL)が80〜200nm
(d)前記シリカ系中空微粒子(A)の平均粒子径(Dpa)が10〜45nm
(e)前記シリカ系中空微粒子(A)の平均粒子径(Dpa)と反射防止膜の膜厚(TL)との比(Dpa/T L が0.05〜0.56である
ことを特徴とする反射防止膜付基材。
A base material with an antireflection film in which a hard coat film and an antireflection film are formed on a base material,
The hard coat film, an average particle diameter becomes from the front surface treated metal oxide fine particles (P) of 5~300nm and matrix component (M H),
(I) the content of the in the hard coat film of the surface-treated metal oxide fine particles (P) (W PH) 50 to 90 wt%,
(Ii) content in said hard coating of the matrix component (M H) (W RH) is 10 to 50% by weight,
(Iii) the amount (W RH) and the content (W PH) and the ratio of (W RH / W PH) is from 0.12 to 1.0,
(Iv) the average thickness of the hard coat film (T H) is 1 to 100 [mu] m,
The antireflection film comprises a silica-based hollow particles (A) and the matrix component (M L),
(A) the content of the antireflection film of the silica-based hollow particles (A) (W PLA) is 5 to 80 wt%,
(B) the content of the antireflection film of the matrix component (M L) (W ML) 20 to 95 wt%,
(C) the thickness of the antireflection film (T L) is 80 to 200 nm,
; (D) an average particle size of the silica-based hollow particles (A) (Dpa) is 10~45Nm,
(E) a the ratio between the average particle diameter (Dpa) and the anti-reflection film having a film thickness of the silica-based hollow particles (A) (T L) ( Dpa / T L) is from 0.05 to 0.56 A base material with an antireflection film as a feature.
前記シリカ系中空微粒子(A)の屈折率が1.10〜1.40であることを特徴とする請求項1に記載の反射防止膜付基材。 Antireflection film with the base material according to claim 1 having a refractive index, characterized in that a 1.10 to 1.40 of the silica-based hollow particles (A). 前記反射防止膜が、さらに平均粒子径(Dpb)が4〜17nmのシリカ系微粒子(B)(中空微粒子、シリカ微粒子、これらの鎖状粒子)を含み、前記シリカ系微粒子(B)の平均粒子径(Dpb)前記とシリカ系中空微粒子(A)の平均粒子径(Dpa)との比(Dpb/Dpa)が0.1〜0.4であることを特徴とする請求項1または2に記載の反射防止膜付基材。 The antireflection film further comprises an average particle diameter (Dpb) is 4~17nm of shea silica-based fine particles (B) (the hollow fine particles, silica fine particles, these chain particles), the average of the silica fine particles (B) to claim 1 or 2 ratio of the average particle diameter (Dpa) particle size (Dpb) wherein the silica-based hollow particles (a) (Dpb / Dpa) is characterized in that 0.1 to 0.4 The base material with an antireflection film as described. 前記反射防止膜中の前記シリカ系中空微粒子(A)と前記シリカ系微粒子(B)の合計の含有量が5〜80重量%前記反射防止膜中の全微粒子中の前記シリカ系微粒子(B)の割合が30重量%以下であることを特徴とする請求項3に記載の反射防止膜付基材。 The total 5-80 wt% content of the silica-based hollow particles (A) and the silica fine particles in the antireflection film (B), the silica fine particles in the total particles in the antireflection film ( The base material with an antireflection film according to claim 3, wherein the proportion of B) is 30% by weight or less. 前記表面処理金属酸化物微粒子(P)が下記式(1)で表される有機珪素化合物で表面処理されていることを特徴とする請求項1〜4のいずれかに記載の反射防止膜付基材。
n−SiX4-n (1)
(但し、式中、Rは炭素数1〜10の非置換または置換炭化水素基であって、互いに同一であっても異なっていてもよい。X炭素数1〜4のアルコキシ基、水酸基、ハロゲン、水素、n1〜3の整数)
The surface-treated metal oxide fine particles (P) are surface-treated with an organosilicon compound represented by the following formula (1), wherein the antireflection film-attached base according to claim 1 is used. Wood.
R n -SiX 4-n (1)
(In the formula, R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different. X is an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, Halogen, hydrogen, n is an integer of 1 to 3)
前記シリカ系中空微粒子(A)および前記シリカ系微粒子(B)が、下記式(2)表される有機珪素化合物で表面処理されていることを特徴とする請求項1〜5のいずれかに記載の反射防止膜付基材。
n−SiX4-n (2)
(但し、式中、Rは炭素数1〜10の非置換または置換炭化水素基であって、互いに同一であっても異なっていてもよい。X炭素数1〜4のアルコキシ基、水酸基、ハロゲン、水素、n1〜3の整数)
The silica hollow particles (A) and the silica fine particles (B) are, according to any one of claims 1 to 5, characterized in that it is surface treated with an organic silicon compound represented by the following formula (2) Base material with antireflection film.
R n -SiX 4-n (2)
(In the formula, R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different. X is an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, Halogen, hydrogen, n is an integer of 1 to 3)
前記表面処理金属酸化物微粒子(P)の球状係数が0.2〜1.0であることを特徴とする請求項1〜のいずれかに記載の反射防止膜付基材。 The surface-treated metal oxide fine particles antireflection film with the base material according to any one of claims 1 to 6, spherical coefficient (P) is characterized in that 0.2 to 1.0. 前記ハードコート膜と前記反射防止膜との界面(接合面)が波状であることを特徴とする請求項1〜のいずれかに記載の反射防止膜付基材。 Antireflection film with the base material according to any one of claims 1 to 7, wherein the interface (bonded surface) between the hard coat film and the antireflection film is wavy. 前記基材がアクリル、ポリカーボネート、シクロオレフィンポリマー(COP)、PET、TACから選ばれる少なくとも1種の樹脂基材であることを特徴とする請求項1〜のいずれかに記載の反射防止膜付基材。 The said base material is at least 1 sort (s) of resin base materials chosen from an acryl, a polycarbonate, a cycloolefin polymer (COP), PET, and TAC, With the antireflection film in any one of Claims 1-8 characterized by the above-mentioned. Base material. 鉛筆硬度が5H以上であることを特徴とする請求項1〜のいずれかに記載の反射防止膜付基材。 Antireflection film with the base material according to any one of claims 1 to 9, pencil hardness, characterized in that at least 5H. (A)表面処理金属酸化物微粒子(P)と、マトリックス形成形分(M H とを含み、前記表面処理金属酸化物微粒子(P)の固形分としての濃度(CPH45〜85重量%、前記マトリックス形成成分(M H )の固形分としての濃度(C RH )が15〜50重量%のハードコート膜形成用塗布液を基材表面に塗布・乾燥して、前記表面処理金属酸化物微粒子(P)の含有量(W PH )が50〜90重量%、マトリックス成分(M H )の固形分としての含有量(W RH )が10〜50重量%のハードコート膜を形成したのち、
(B)シリカ系中空微粒子(A)とマトリックス形成成分と溶媒とを含み前記シリカ系中空微粒子(A)の平均粒子径(Dpa)が10〜45nm、前記シリカ系中空微粒子(A)の固形分としての濃度が0.25〜9重量%マトリックス形成成分の固形分としての濃度が0.75〜9.5重量%で、全固形分濃度が1〜10重量%の反射防止膜形成用塗布液を前記ハードコート膜表面に塗布し乾燥して、反射防止膜を形成することを特徴とする反射防止膜付基材の製造方法。
(A) and surface-treated metal oxide fine particles (P), and a matrix-forming solid content (M H), the concentration of the solid content of the surface-treated metal oxide fine particles (P) (C PH) is 45 A coating liquid for forming a hard coat film having a concentration (C RH ) of 15 to 50% by weight as a solid content of the matrix-forming component (M H ) is applied to the substrate surface and dried , A hard coat film having a treated metal oxide fine particle (P) content (W PH ) of 50 to 90% by weight and a matrix component (M H ) content (W RH ) of 10 to 50% by weight. After forming
(B) a silica-based hollow particles (A) and a solvent matrix-forming component, wherein the average particle size of the silica-based hollow particles (A) (Dpa) is 10~45Nm, solid of the silica-based hollow particles (A) concentration as a minute from 0.25 to 9 wt%, at a concentration of 0.75 to 9.5% by weight as solids of the matrix-forming component, the total solid concentration for preventing film formation reflection of 1-10 wt% A method for producing a substrate with an antireflection film, which comprises applying a coating solution to the surface of the hard coat film and drying to form an antireflection film.
前記ハードコート膜の下記条件で測定したときのカーリング特性が5mm以下であることを特徴とする請求項11に記載の反射防止膜付基材の製造方法。
14cm×25cm×40μm(厚み)のTACフィルム基材上に厚みが12μmのハードコート膜が形成できるようにハードコート膜形成用塗布液を塗布し、20時間静置し、その後、フィルムを10cm×10cmサイズにカットし、塗布面を下にしてフィルムを平板上に置き、カーリング(湾曲)して浮上した基材の頂点の平板からの高さ。
The method for producing a base material with an antireflection film according to claim 11 , wherein the curling property of the hard coat film is 5 mm or less when measured under the following conditions.
A coating liquid for forming a hard coat film was applied on a TAC film substrate having a thickness of 14 cm × 25 cm × 40 μm (thickness) so that a hard coat film having a thickness of 12 μm could be formed, and allowed to stand for 20 hours. The height from the flat plate at the apex of the substrate which was cut into a size of 10 cm, placed on a flat plate with the coating surface down, and curled (curved) and floated.
前記ハードコート膜形成用塗布液を塗布した後、乾燥したときの塗膜の収縮率が25%以下であり、硬化したときの塗膜の収縮率が10%以下であり、合計の収縮率が35%以下であることを特徴とする請求項11または12に記載の反射防止膜付基材の製造方法。 After applying the hard coat film-forming coating solution, shrinkage of the coating film upon drying is 25% or less, and the coating of shrinkage of not more than 10% when cured, the total shrinkage It is 35% or less, The manufacturing method of the base material with an antireflection film of Claim 11 or 12 characterized by the above-mentioned. 前記シリカ系中空微粒子(A)の屈折率が1.10〜1.40あることを特徴とする請求項11に記載の反射防止膜付基材の製造方法。 The refractive index of the said silica type hollow microparticle (A) is 1.10-1.40 , The manufacturing method of the base material with an antireflection film of Claim 11 characterized by the above-mentioned. 前記反射防止膜形成用塗布液が、さらに、平均粒子径(Dpb)が4〜17nmのシリカ系微粒子(B)を含み、前記シリカ系微粒子(B)の平均粒子径(Dpb)と前記シリカ系中空微粒子(A)の平均粒子径(Dpa)との比(Dpb/Dpa)が0.1〜0.4あることを特徴とする請求項11に記載の反射防止膜付基材の製造方法。 The antireflection film-forming coating liquid further comprises an average particle diameter (Dpb) is 4~17nm silica-based fine particles (B), the average the silica particle size (Dpb) of the silica fine particles (B) the average ratio of particle diameter (Dpa) of the hollow fine particles (a) (Dpb / Dpa) are provided methods for producing the anti-reflection film with the base material according to claim 11, characterized in that 0.1 to 0.4 . 前記シリカ系中空微粒子(A)および前記シリカ系微粒子(B)が、下記式(3)で表される有機珪素化合物で表面処理されていることを特徴とする請求項15に記載の反射防止膜付基材の製造方法。
n−SiX4-n (3)
(但し、式中、Rは炭素数1〜10の非置換または置換炭化水素基であって、互いに同一であっても異なっていてもよい。X炭素数1〜4のアルコキシ基、水酸基、ハロゲン、水素、n1〜3の整数)
The silica hollow particles (A) and the silica fine particles (B) is an anti-reflection film according to claim 15, characterized in that it is surface-treated with an organosilicon compound represented by the following formula (3) A method for producing a substrate.
R n -SiX 4-n (3)
(In the formula, R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different. X is an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, Halogen, hydrogen, n is an integer of 1 to 3)
前記反射防止膜形成用塗布液中のマトリックス形成成分が有機樹脂系マトリックス形成成分であることを特徴とする請求項11に記載の反射防止膜付基材の製造方法。 The method for producing a substrate with an antireflection film according to claim 11 , wherein the matrix forming component in the coating liquid for forming the antireflection film is an organic resin matrix forming component. 前記反射防止膜形成用塗布液中のマトリックス形成成分が分散用有機樹脂(A)および/または硬化用有機樹脂(B)を含むことを特徴とする請求項17に記載の反射防止膜付基材の製造方法。 18. The substrate with an antireflection film according to claim 17 , wherein the matrix-forming component in the coating liquid for forming the antireflection film contains an organic resin for dispersion (A) and / or an organic resin for curing (B). Manufacturing method. 前記分散用有機樹脂(A)が1〜2個の官能基を有する紫外線硬化型樹脂モノマーないしオリゴマーであり、前記硬化用有機樹脂(B)が3個以上の官能基を有する紫外線硬化型樹脂モノマーないしオリゴマーであることを特徴とする請求項18に記載の反射防止膜付基材の製造方法。 The dispersion organic resin (A) is an ultraviolet curable resin monomer or oligomer having 1 to 2 functional groups, and the curable organic resin (B) is an ultraviolet curable resin monomer having 3 or more functional groups. It is thru | or an oligomer, The manufacturing method of the base material with an antireflection film of Claim 18 characterized by the above-mentioned. 前記分散用有機樹脂(A)および前記硬化用有機樹脂(B)の有する官能基が(メタ)アクリレート基、ウレタン(メタ)アクリレート基、アルキレンオキサイド変性(メタ)アクリレート基から選ばれる少なくとも1種であることを特徴とする請求項18または19に記載の反射防止膜付基材の製造方法。 The functional group possessed by the organic resin for dispersion (A) and the organic resin for curing (B) is at least one selected from a (meth) acrylate group, a urethane (meth) acrylate group, and an alkylene oxide- modified (meth) acrylate group. 20. The method for producing a substrate with an antireflection film according to claim 18 or 19 , wherein the substrate has an antireflection film. 前記ハードコート膜形成用塗布液を塗布、乾燥し、前記反射防止膜形成用塗布液を塗布、乾燥し、ついで紫外線照射して同時に硬化することを特徴とする請求項11に記載の反射防止膜付基材の製造方法。 Applying the hard coat film-forming coating solution, dried, coated with the antireflection film-forming coating solution, dried, and then the anti-reflection film according to claim 11, characterized in that the cured simultaneously irradiated with ultraviolet rays A method for producing a substrate.
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KR1020167026821A KR102379944B1 (en) 2014-03-31 2015-03-30 Coating liquid for forming transparent coating and method for producing said coating liquid, organic resin-dispersed sol, and substrate with transparent coating and method for producing said substrate
PCT/JP2015/059981 WO2015152171A1 (en) 2014-03-31 2015-03-30 Coating liquid for forming transparent coating and method for producing said coating liquid, organic resin-dispersed sol, and substrate with transparent coating and method for producing said substrate
CN201580017788.XA CN106164190B (en) 2014-03-31 2015-03-30 Coating liquid for forming transparent film and method for producing same, organic resin dispersion sol, substrate with transparent film and method for producing same
TW104110415A TWI670335B (en) 2014-03-31 2015-03-31 Coating liquid for forming transparent coating film and method for producing the same, organic resin dispersant sol, and substrate with transparent coating film and method for producing the same

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