[OOOlj
The present invention ):eiates to hydrophilic modified acrylic resin films excellent in antifogging pi:operties, antifouling properties and transparency, and to stacks having 10 the modified acrylic resin films.
BACKGROUND ART [0002]
There have recently been increasing demands that 15 substrates formed of organic materials such, as plastics and inorganic materials such as glass be improved in terms of antifogging properties and antifouling properties. [0003]
To solve the fogging problems, a method has been proposed 20 in which an antifogging coating containing a reactive
surfactant and an acrylic oligomer is applied to provide enhanced hydrophilicity and water absorption (see, for example, Non Patent Document 1) . The fouling problems have been addressed by methods in which the hydrophilicity of the surface
of materials is enhanced so that fouling such a^ hydrophobic substances in the air which have become attached to surfaces such as e^iterior walls C3.n be detached and removed from the surfaces by water spray or rainfall (see, for example, Kon 5 Patent Documents 2 and 3). [0O04]
Further, hydrophiiic materials have been proposed in which a crosslinkable polymerizable monomer composition is applied onto the surface of a substrate and is incompletely
10 polymori^ed while controlling the dose of UV irradiation to form a crosslinlced polymer, and subseguently a hydrophiiic monomer is applied and UV rays are applied again to block- or graft-polymerize the hydrophiiic monomer to the surface of the crosslinked polymer (Patent Document 1 and Patent Document 2) .
15 [0005]
However, this simple block or graft polymerization of a hydrophiiic monomer to the surface of a substrate only attaches the hydrophiiic groups to the surface, resulting in low durability. Thus, the hydrophiiic materials have drawbacks in
20 that they cannot withstand long-term use, [0006]
To solve the above problem, the present inventors have proposed a monolayer film in which specific anionic hydrophiiic groups have a concentration gradient (an uneven distribution)
between the inside of the film and the film surface and the anionic hydrophilic groups are present in a higher concentration near the surface fPatent Document 3 and Patent Document 4). 5
CITATION LIST PATENT LirtlRATURE [0007J
Patent Document 1; JP-A-2O01-98O07 10 Patent Document 2: JP-A-2011-229734 Patent Document 3: WO 2007/06^003 Patent Document 4: WO 2012/014829 NON PATENT LITERATURE [0008] 15 Non patent Document 1: TREND, annual research report by TOAGOSEI CO., LTD., 1999, February issue, pp. 39-44
Non Patent Document 2: Koubunshi [Polymers), ^4(5), p. 307
Non Patent Document 3: Mirai Sairyou (Future materials), 20 2(1), pp. 36-41
SUMMARY OF INVENTION TECHNICAL PROBLtlM [0009]
An object of the present invention is to improve the durability while further Increasing the hydrophilicity of the previous applications of the present inventors (Patent Document 3 and Patent Document 4) and thereby to provide 5 hydrophilic films which exhibit high performances such as antifogging properties, antifouling properties and anti-condensation properties and can withstand long-term use and also to provide staclcs having the hydrophilic films.
10 SOLUTION TO PROBLEM [0010]
To achieve the above object, the present inventors have carried out e^^tensive studies and have found that hydrophilicity may be further improved and also durability is
15 increased by designing an acrylic resin film having anionic hydrophilic groups such that the concentration of the anionic hydrophilic groups on a surface is higher than the concentration of the anionic hydrophilic groups at a depth half the film thickness from the surface of the acrylic resin film, and also
20 by treating the surface of the acrylic resin film with a compound (A) which has in the molecule thereof one or more anionic hydrophilic groups and one or more groups selected from groups having a polymerizable carbon-carbon double bond, amino groups, mercapto groups and hydroxyl groups. Based on the finding, the
present inventors have completed the invention. [0011]
The present invention resides in a modified acrylic resin film obtained by treating a surface of an acrylic resin film 5 having anionic hydrophilic groups with a compound (A), the acrylic resin film being such that the concentration of. the anionic hydrophilic groups on the surface Is higher than the concentration of the anionic hydrophilic groups at a depth half the film thickness from the surface of the acrylic resin film, 10 the compound (A) having in the molecule thereof one or more anionic hydrophilic groups and one or more groups selected from groups having a polymerizable carbon-carbon double bond, amino groups, mercapto groups and hydroxyl groups.
15 ADVANTAGEOUS Et'FECTS OF INVENTION
[0012]
The hydrophilic films of the invention achieve
improvements in hydrophilicity and durability and exhibit high
performances such as antifogging properties, antifouling 20 properties and anti-condensation properties for a long term
of use.
BRIEF DESCRIPTION OF DRAWING [00131
[Fig. 1] Fig. 1 is a view illustrating the preparation of samples in Examples-
DESCRIPTION OF EMBQDlMh^NTS 5 [0014]
A modified acrylic res in film of the invention is obtained by treating an acrylic resin film hEXving anionic hydrophilic groups. Specifically, the inventive modified acrylic resin film is obtained by treating a surface of an acrylic resin film
10 having anionic hydropliilic groups in a highes: concentration on the surface than afc a depth half the film thickness from the surface of the acrylic resin film, with a compound (A) having in the molecule thereof one or more anionic hydrophilic groups and one or more groups selected from groups having a
15 poiymerizable carbon-carbon double bond, amino groups, mercapto groups and hydroxyl groups. [0015]
[Acrylic resin films having anionic hydrophilic groups in higher concentration on the surface than at depth half the film
20 thickness from tho surface]
The acrylic resin films used in the invention are not limited as long as the acrylic resin films are such that the concentration of the anionic hydrophilic groups on the surface is higher than the concentration of the anionic hydrophilic
groups at a depth half the film thickness from the surfEice-In the specification, such filmy are otherwise written as the "films having a gradient of anionic hydrophilic groups (gradient films)". Examples of such films having a gradient 5 of anionic hydrophilic groups inc^lude highly hydrophilic films in which the concentration of anionic hydrophilic groups on the surface is increased by evaporating the solvent (Patent Document 3 and Patent Document 4) , and such films may be suitably used as the films to be treated in the invention, here, the
10 anionic hydrophilic groups indicate hydrophilic functional groups selected from sulfonic groups, carboxyl groups and phosphoric groups. Of these, sulfonic groups are particularly preferable because higher hydrophilicity may be imparted to the surface,
15 [0016]
TOF-SIMS is used in the analysis of the anionic hydrophilic groups in the acrylic resin film fthe film having a gradient of anionic hydrophilic groups) used in the invention in which the concentration of the anionic hydrophilic groups
20 on the surface is higher than the concentration of the anionic hydrophilic groups at a depth half the film thickness from the surface. The property that the concentration of the anionic hydrophilic groups is higher on the surface than at a depth half the film thickness from the surface is usually represented
by the anion concentration ratio Sa/r)a (the ratio of the anion concentration Sa at the film surface to tho anion concentration Da at a depth Iialf the film thick.nGss from the suirface) . Any ratio 3a/Da ej
:JVLUla [3), those compounds in which v = w - x 0 represent a preferred embodiment. 10 [0045J
Typical examples of the compounds represented by General Formula {S ) include (meth)acrylic acid, sodium (meth)aerylate, potassium (meth)acrylate, (meth)acryloyloxyethylcarboxylic acid, sodium tmath)aeryloyloxyethylcarboxylate salt, 15 (inethJ acrylamidoethylcarboxylic acid, allylcarboxylic acid, isopropenylcarboxylic acid, styrylcaj:boxylic acid, thioglycolic acid, sodium thioglycolate, 3-mercaptopropionic acid, sodium 3-mercaptopropionate, L-aspartic acid, potassium L-aspartate, sodium D-aspartate, p-alanine sodium, L-arginine 2 0 potassium, glycine sodium, sodium L-glutamate, L-cystine potassium, L-serine potassium and glyeylglycine sodium. [0046]
Of the compounds represented by General Formula (^ ) , more preferred compounds are represented by General Formula £9):
[OOdV] [Chem. 9]
(9)
004S]
5 {In Formula {9), Dj ia a (meth)acryloyloKy group, a
(meth)acryioylthio group, a (meth)acrylamide group, a vinyl group, an allyl group, an isopropenyl group, a styryl group, a mercapto group, an amino group, a methylamino group or an ethylamino group; Z is a hydrogen ion, an ammonium ion, an amine
10 ion, an ailtali metal ion or an alkaline earth metal (1/2 atom) ion; Ri to R^ are independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an allcoKy group having 1 to 6 carbon atoms; a and b represent 1 or 2, and a h b = 3; c is an integer of 1 to 20; d is an integer of 1 to 10; when c is
15 2 or greater, R, s or R?E may be the same or different from each other; when d is 2 or greater, Ris or R2S may be the same or different from each other; when a is 2, DtS, RiS or R^s may be the same or different from each other; and when b is 2, Zs may be the same or different from each other.)
20 [0049]
Typical examples of the compounds represented by General Formula (9) include sodium fmeth)acryloyloxymothylphosphate,
(meth) 3cryloyloxyethylphosphoric acid, sodium (meth)acryloyloxyethylphoHphate, potassium bis((meth)acryloyloxyethyl}phosphate, potasHium 5-(meth)acryloyloxy-3"OxapenLylpho3phate, sodium 5 B-Emeth)acryloyloxy-3,S-dioxaoctylphosphatc, potassium 11- (meth) acryloylo;:iy-3, 6, 9-trioxaundecylphosphate and sodium styryloxyethylphosphate, [0050]
Examples of the compounds represented by General Formula
10 (5) include 3^aminobenzenesulfonic acid, sodium
^-aminobenzenesuifonate salt, 5-aminotoluene-2-sulfonic acid, sodium 4-amino-3-methoxybenzenesulfonate salt, potassium 3-aminO"4-mGthoxybenzenesulfonate salt, monopotassium 7-amino-l,3-naphthalenedisulfonate salt, monosodium
15 8-amino~l,3-naphthalenedisulfon3te salt, disodium
7-amino-l,3,S-naphthalenetrisulfonate salt, trisodium 8-amino-l,3,S-naphthalenetrisulfonate salt, sodium 4-hydroxybGnzenesulfonate salt, potassium 4-hydroxy-3-methoxybenzenesulfonate salt, disodiuin
20 1,2-dihydroxy-3,5-benzenedlsulfonate salt, dipotassium 2-hydroxy-6, S-^naphthalenesulfonate salt and trisodium 8-hydroxypyrene-l,3,6-trisulfonate salt. Of these compounds, sodium '1-aminobenzenesulfonate salt, sodium 5-aminotoluene-2-sulfonate salt, monopotassium
7-amino'-l, 3-naphthalenedisulfonate salt, trisodium 8-amino-l,3,6-naphth£3lenetrisulfonate salt and sodium 4-hydroxybenzenesulfonate salt are preferable. [OOSiJ 6 Examples of the compounds represented by General Formula [6} include sodium l-aminoanthraquinonG-2-sulfonate, sodium 1-aminoanthraquinone-^-sulfonate, sodium 1-aminoanthraquinone-8-sulfonate, sodium l"amino~4-bronioanthraquinono"2"sulfonate and sodium
10 1-amino-2, 'l-dihydrQxyanthraquinone-3-5ulfonate. Of theso compounds, sodium l~amino-4-bromoanthraquinone-2-sulfonate 3.nd sodium 1-amino-2, 4-dihydroxyanthrs qui none-3-sulfonate are preferable. [0052]
15 [Treatment with compounds (A)]
A solution of the compound (A) having an anionic hydrophilic group is applied to the acrylic resin film having a higher concentration of anionic hydrophilic groups on the surface than at a depth half the film thicltness from the surface.
20 A radiation or heat is then applied to allow the compound [A) to be grafted to the surface, and thereby the concentrations of the anionic hydrophilic groups on the surface and in an inner portion near the surface are increasod. In this manner, a further increase in hydrophilicity may be obtained snd
antifogging properties may bo improved. A typical example of the grafting reaction of the compound {h) to the gradient film will bo described below. [0053] 5 [Chem. 10]
lo 17 fuTLC t icoL a 1
njv>An Haat aUEfacc
pPOiKi
Hcai fiit:£n<»
SO3K
(A3) 0=.0 0^0
SOaPte
Enlatge
\An/v'
Haar akivfoi^
HssE autfBC#
l^jj^SO^?
HN
Haav diicfDCc
MaDgS
UN
Ucflc tiicfn(»
SOjK
j%A^
Bean ^ux'faca
[0054]
The acrylic resin films used in the invention which have a higher concentration of the anionic hydi:ophilic groups on the surface than at a depth half the film thickness from the 5 surface may be obtained by the method descjribed in Patent Document 3 or Patent Document 4. For example, the films may be produced by a production method including a step of preparing a mixture including a polyvalent monomer (II) having two oi: more fmeth)acryloyl groups, a compound (AM having at least
10 one anionic hydrophilic group and at least one group selected from groups having a polymerizable carbon-carbon double bond, amino groups, raercapto groups and hydroxyl groups Ethis compound is different from the polyvalent monomer (II)) and a solvent including, for example, a compound with a solubility
15 parameter o" fcal/cm"^) of not less than 9.3, and preferably not less than 9,5; a step of applying the mixture onto at least one side of a substrate surface; a step of removing at least part of the solvent from the mixture applied; and a step of polymerizing the mixture resulting from the above steps . That
20 is, a method for producing the modified acrylic resin film preferably includes steps of forming the aforementioned acrylic resin film on a substrate. [0055]
For example, the acrylic films used in the invention may
be obtained by a single application of the raij^ture containing the compound (S' ) and the poly functional monomer 1II) . Films produced in this manner will be sometimes referred to as "monolayer films". In the invention, the acrylic film is 5 preferably a monolayer film, [0056]
Alternatively, the substrate may be removed from the stack of the substrate and the acrylic resin film obtained by the aforementioned stops, and the acrylic resin film may be 10 attached or stacked as a hydrophilic film onto another substrate, [0057]
In the polyvalent monomers {II) having two or more tmeth)acryloyl groups, examples of the (meth)acryloyl groups 15 includo (meth)acryloyloxy groups, fmoth)acryloylthio groups and fmethj acryiamide groups, with fmeth) acryloyloxy groups and (meth)acryloylthio groups being particularly preferable. Preferred examples of the polyvalent monomers {II) include compounds having one or more hydroxyl groups and two or more 20 (meth)acryloyl groups in the molecule, compounds having one or more ether bonds or thioether bonds and two or more tmeth) acryloyl groups in the molecule, compounds having, other than (meth)acrylate groups, one or more ester bonds and two or more (meth) acryloyl groups in the molecule, compounds having
ono or more Eiiicyolic or aromatic ring strijctuces and two or more (meth)acryloyl groups in the molecule, and compounds having one or more heterocyclic structures and two or more (meth)acryloyl groups in the molecule. 5 [00531
More specific examples include the compounds described in [0057] to [0150] of Patent Document 3 (WO 2007/064003, applicant: MITSUI CHEMICALS, INC., inventors: Koju OKfiZAKI et al. ) . The preferred embodiments of the compounds described in
10 Patent Document 3 also apply to the present invention. [0059J
Examples of the compounds (A' ) having at least one anionic hydrophilic group and at least one group selected fi:ora groups having a polymerlzabie carbon-carbon double bond, amino groups,
15 meccapto groups and hydroxyl groups include compounds similar to the compounds (A) described later. Compounds similar to the compounds (A) represented by General formulae (1) to (6) are preferable. f0060j
20 In addition to the polyvalent monomer (IIj , the compound (A'} and the solvent, the production of the aojrylic resin films may optionally involve additives such as polymerization initiators, polymerisation accelerators, UV absorbers, hindered amine light stabilizers (HALS), catalysts^ UV
absorbing agents, radical scavengers, internal release agents, antioxidants, polymerization inhibitors, pigments, binders and leveling agents. The amount of the solvent is not particularly limited, but is usually not less than 1 part by 5 weight and not more than 99 parts by weight, preferably not less than 5 parts by weight and not more than 95 parts by weight, &nd more preferably not less than 10 parts by weight and not moro than 90 parts by weight with respect to 100 parts by weight of the total of the additives, the polyvalent monomer {IIJ,
10 the compound (A' ) and the solvent. At this stage, the mixture may further contain a solvent having a solubility parameter out of the aforementioned range as long as the advantageous effect of the invention can be achieved. After the step of removing at least part of the solvent from the mixture applied^
15 namely, immediately before the polymerization, the ratio of (total residual solvent) to (mixture applied - solvent removed) is preferably not more than 10 wt%, more preferably not mere than 9 wt%, still more preferably not more than 5 wt%, and particularly preferably not more than 1 wt%.
20 i0061]
The acrylic films obtained by ^n appropriate method, for example, the method described above, will be usually such that the concentration of the anionic hydrophilic groups increases in the direction from a position at a depth half the film
thicJcness from the surface, to the surface of the film. [0062]
Regarding the compounds (A') used in the gradient films, (meth)acrylates having an anionic hydrophilic group are 5 preferably hydrophi.lic compounds exhibiting higher solubility in highly polar solvents such as alcohols and water, rather than being amphiphilic compounds. The compounds (A'J desirably have a solubility of not more than 24 wt%, preferably not more than 10 wt%, and more preferably not more than 3 wt% 10 in a mixed solvent of cyclohexano:toluene = 5rl {by weight) at 25°C. Such compounds are advantageous in that films having the aforementioned degree of gradient (Sa/Da) may be obtained easily. [0063] 15 Preferred examples of the coicipounds (A'j having an
anionic hydrophilic group include compounds represented by General Formula (10): [006^] [Chem. 11j
20
o
ij
Ar
o ° (10)
[0065]
fin General Formula (10) , J is a hydrogen atom or a methyl
group; R is a divalent aliphatic hydrocarbon group having 1. to 600 carbon atoms and may include one or more groups selected from aromatic rings, al.lcyclic groups, ether groups and oster groups; and Z is a hydrogen ion, an ammonium ion, an amine i.on, 5 an alkiali metal ion or an alkaline earth metal (1/2 atomj ion) , compounds represented by General Formula (11): [0066] [Chem. 12]
(11)
10 [0067]
(in General Formula (11) , J is a hydrogen atom or a methyl group; R is a divalent aliphatic hydrocarbon group having 1 to 60O carbon atoms and may include one or more groups selected from aromatic rings, alicyclic groups, ether groups and ester
15 groups; Z is a hydrogen ion, an ammonium ion, an amine ion, an alkali metaJ ion or an alkaline earth metal (1/2 atom) ion; and nn is 0 or 1), and
compounds represented by General Formula fl2): [0068]
20 tChem. 13]
o
O-R-0
J a
-P' II
0
o-z
(IS
[0069]
(in General Formula (12) , J is a hydrogen atom or a moLhyl group; R is a divalonl: aliphatic hydrocarbon group having 1 5 to 600 carbon atoms and may include one or more groups selected from aromatic rings, alicyclic groups, ether groups and ester groups; Z is a hydrogen ion, an ammonium ion, an amine ion, an alkali metal Ion or an alkaline earth metal (1/2 atom) ion; a and b independently represent 1 or 2, and a ^ b ^ 3; when 10 a is 2, Js or Bs may be the same or different from each other; and when b ia Z, Zs may be the same or different from each other) . [0070]
Of the compounds represented by General Formulae (10) to (12), the compounds of General Formula (10) are relatively 15 preferable. [0071]
Of the compounds represented by General Formula (10), more preferred compounds are represented by, for example, General Formula (13): 20 [0072]
Chem. 14]
R4/mmO ^^3^
[0073]
(in General Formula [13) , J is a hydrogen atom or a methyl gj:oup; Rj and R^ independently represent a hydrogen atom, a 5 methyl group or an ethyl group; Z is a hydrogen ion, an ammonium ion, an amine ion, an alkali metal ion or an alltaline earth metal (1/2 atom) ion; mm is an integer of 1 to 20; when mm is 2 or greater, R^s or R^s may be the same or different from each other; and in preferred embodiments, mm is I to 10, and 10 particularly 1 to 3) , and
compounds represented by General Formula (14)i [00741 [Chem. 15]
o
II
■s~o-z
f^/mmJiiO ^^^j
15 [0075]
fin General Formula (14) , J is a hydrogen atom or a methyl gro\xp; Rj and R4 independently represent a hydrogen atom, a methyl group or an ethyl group; Z is a hydrogen ion, an ammonium ion, an amine ion, an alkali metal ion or an al};aline earth
20 metal (1/2 atom) ion; mm is an integer of 1 to 20; li is 2 to
10; and when mm is 2 or greater, R^s or R^a may be the same or
different from each other).
[00761
In the production of the acrylic films (the gradient 5 films) used in the invention, the polymerization may be performed by, for example, the application of radiations. [0077]
Examples of the substrates used in the invention optionally as required include substrates made of inorganic 10 materials such as glasses, silicas, metals and metal oxides, substrates made of organic materials such as polymethyl methacrylates, polycarbonates, polyethylene terephthalates, polyethylenes, polypropylenes, polystyrenes, polyurethane resins, epoxy resins, vinyl chloride resins, silicone resins, 15 paper and pulps, and these inorganic or organic material substrates having a cured coating layer on the surface. [0078]
In order to activate the substrate surface as required, the surface of these substrates may be subjected to physical 20 or chemical treatments such as corona treatment, ozone
treatment, low-temperature plasma treatment using a gas such as oxygen gas or nitrogen gas, glow discharge treatment, oxidation treatment with agents such as chemicals, and flame Lreatment. Instead of or in addition to such a treatment, the
substratG surface may be subjected to primer treatment, undercoating treatment or anchor coating treatment. [0079]
Examples of the coating agents used in the primer 5 treatment, the undercoating treatment and the anchor coating treatment include coating agents containing, as the main components of vetiicl.es, resins such as polyester resins, polyamide resins, polyurethane resins, opoxy rosins, phenolic resins, (meth)acrylic resins, polyvinyl acetate resins, 10 polyolefin resins including polyethylenes and polypropylenes as well as copolymers thereof or modified resins thereof, and cellulose resins. The coating agents may be any of solvent-based coating agents and aqueous coating agents. [0080] 15 Of these, preferred coating agents are:
modified polyolefin coating agents, ethyl vinyl alcohol coating agents, polyethyleneimine coating agents, polybutadiene coating agents, polyurethane coating agents; polyester polyurethane emulsion coating agents, 20 polyvinyl chloride emulsion coating agents, urethane acrylic emulsion coating agents, silicon acrylic emulsion coating agents, vinyl acetate acrylic emulsion coating agents, acrylic emulsion coating agents;
styrene/butadiene copolymer latex coating agents,
aorylonitrile/butadiene copolymer latex coating agents, methyl methacrylate/butadiene copolymer latoz coating agents, chloroprene latex coating agents, rubber latex coating agents containing polybutadiene latex, polyacrylate ester latex 5 coating agents, poiyvinylideno chloride latex coating agents, polybutadiene latex coating agents, and coating agents which are latexes or dispersions resulting from the carboxylic acid modification of the resins in the above latex coating agents. [0081] 10 For example, these coating agents may be applied by
methods such as gravure coating methods, reverse roll coating methods, Icnife coating methods and kiss-roll coating methods. The amount of coating to the substrate is usually 0,05 g/m^ to 5 g/m^ on dry basis. 15 [0082]
Of these coating agents, polyurethane coating agents are more preferable. Tlie polyurethane coating agents have a urethane bond in the main chain or a side chain of the resin contained in the coating agents . For example, the polyurethane 20 coating agents contain a polyurethane obtained by reacting a polyol such as a polyester polyol, a polyether polyol or an acrylic polyol, with an isocyanate compound. [0083]
Of the polyurethane coating agents, excellent adhesion
is advantageously provided by polyiiirethane coating agents obtained by mixing a polyester polyol such, as a condensed polyester polyol or a lactone-based polyester polyol with an isocyanate compound such as tolylene diisocyanate, 5 hexamethylene diisocyanate or xylene diisocyanate. [0084]
The polyol compounds and the isocyanate compounds may be mixed with each other by any methods without limitation. The mixing ratio is not particularly limited. When, however, the 10 amount of the isocyanate compound is excessively small, curing failure may be caused. Thus, the equivalent ratio of the OH groups of the polyol compound to the HCO groups of the isocyanate compound is preferably in the range of 2/1 to 1/40. [0085] ].5 The substrate in the invention may have a surface that has been activated by the aforementioned treatment. [0086]
The acrylic film used in the invention is usually such that the concentration of the anionic hydrophilic groups on 20 one side of the surface is higher than the concentration of the anionic hydrophilic groups at a depth half the film thickness from the surface. When the substrate is present, the concentration of the anionic hydrophilic groups on the side of the surface opposite to the substrate is usually higher than
the concentration of the anionic hydrophilic groups at a depth half the film thiclcnoss from the surface. In other words, the acrylic resin film is usually such that the concentration of the anionic hydrophilic groups on the aide of the surface 5 opposite to the side adjacent to the substrate is higher than the concentration of the anionic hydrophilic groups at a depth half the film thickness from the surface of the acrylic resin film, [008V1
10 In the invention; the ratio Sa/Da is preferably not less than 1.2, and more preferably not less than 1.3. While the upper limit is not limited, the ratio is usually 20 or less. In the invention, the ratio Sa/Da of the acrylic film is a value prior to the treatment with the compound (A) . In the case where
15 the film is treated with the compound fA) while the
polymerization is still incomplete 3s will be described later, the ratio Sa/Da is a value of the incompletely polymerized mixture. [0063]
20 The treatment in the invention is usually carried out by applying a solution of the compound (A) and optionally a surfactant (a leveling agent) in a solvent to the surface of the gradient film, thereafter drying the solvent, then applying a radiation or heat to the coating to perform graft reaction,
and finally removing the compound (A) that has not been involved in the graft reaction by washing or the like. The solution may be applied after the acrylic film {the gradient film) has been irradiated with a radiation or the like to generate radicals. 5 Alternatively, the acrylic film may be produced without
completing the polymerization and the solution may be applied to such a film. To render the polymerization incomplete, for example, the dose of radiation may be appropriately decreased from the level required for complete curing.
10 [0089]
The degree of polymerization of the (meth)acrylic resin is usually calculated from the amount of residual (meth) acrylic groups. The residual (meth)acrylic groups may be quantitatively determined by analyzing the >C=CH2 peak (808
15 cm"^) by IR. [0090]
In general, films having a degree of polymerization of (meth) acrylic resins that is as low as about 10 mol% or below often tend to incur problems such as the breakage of the acrylic
20 resin films during the graft treatment and the elution in the graft treatment liquid of the hydrophilic (meth)acrylate (A') having anionic hydrophilic groups with a gradient on the film surface and inside near the film surface. On the other hand, films that have been polymerized approximately to the same level
as the usual radiation polymerization, that is, filniH having a polymerization degree of, for eKample, moire than G0% disadvantageonsly tend to incur a decrease in the grafting rate (a decrease in the graft amount) duo to the lowering of the 5 polymer radical concentration at the su3:face and inside near the surface. [0091]
Accordingly, the degree of polymerization of the Emeth)acrylic groups in the acrylic resin gradient films to 10 be graft treated ia preferably approximately 3 to 60 mol%, more preferably 20 to 60 mol%, and still more preferably 35 to 55 mol%, [0092j
From the viewpoint of solvent properties, the solvents 15 used in the invention are preferably highly polar solvents. Examples include alcohols such as methanol, ethanol, isopropanol flPA), n-propanol, n-butanol, ethylene glycol monomethyl ether (EGM) and 1,2-propylene glycol monomethyl ether (EGM) , nitrogen-containing solvents such as acetonitrile 20 and N,N-dimethylformaTnide {liJMFj , sulfur-containing solvents such as dimethylsulfoxide (DMSO) and sulfolane, water and mixtures of these solvents. Of these, alcohols, water and mixtures of these solvents are preferably used in light of relatively high solvent properties. From the viewpoint of
safety, ethanol, water and a mixture of those solvents are more
preferable.
[00931
The concentration of tho compound (A) dissolved in the 5 solvent may vary depending on the solvent selected, and is approximately 0.001 wt% to the saturated solubility, preferably 0.01 to 50 wt^, more preferably 0,01 to 20 wt% and still more prefej:ably 0.1 to 10 vt%. [0094]
10 Surfactants (leveling agents) may be added as required
mainly for the purpose of preventing the cissing of the coating liquid. Examples include carboxylate salts such as alJcylcarboxylic acids and alkali metal or alkaline earth metal salts thereof, and polyoxyethylene alkylether carboxylic acids
15 and alkali metal or alkaline earth metal salts thereof;
sulfonate salts such as alkylbenzenesulfonic acids and alkali metal or alkaline earth metal salts thereof, alkylnaphthalenesulfonic acids and alkali metal or alkaline earth metal salts thereof, polycondensates of alkali metal or
20 alkaline earth metal salts of alkylnaphthalenesulfonic acids with formalin, polycondensates of alkali metal or alkaline earth metal salts of melaminesulfonic acids with formalin, dialkylsulfosuccinate esters and alkali metal or alkaline earth metal salts thereof, ct-olefinsulfonic acids and alkali
metal or alkaline earth metal salts thereof, and N-acylsulfonic acids and alkali metal or alkalino oarth metal salts thereof; sulfate ester salts such as sulfonated oils, alkali metal or alkaline earth metal salts of alkylsulfuric acids, alkali metal 5 or alkaline earth metal salts of alkylether sulfuric acids, alkali metal or alkaline earth metal salts of polyoxyethylene alkylether sulfuric acids, and alkali metal or alkaline earth metal salts of alkylamide sulfuric acids; phosphate ester salts such as alkylphosphoric acids and alkali metal or alkaline earth
10 metal salts thereof, polyoxyethylene alkylether phosphoric acids and alkali metal or alkaline earth metal salts thereof, and alkylaryl ether phosphoric acids and alkali metal or alkaline earth metal salts thereof; anionic surfactants such as aliphatic amine salts, quaternary ammonium salts,
15 bengalkonium chlorides, benzethonium chlorides, pyridinium salts and imidazolinium salts; amphoteric surfactants such as carboxybetaine, aminocarboxylate salts, imidazolinium betaine, lecithin and alkyiamine oxides;
nonionic surfactants such as polyoxyethylene alkyl and
20 aryl ethers, polyoxypropyiene alkyl and aryi ethers,
polyoxyethylene alkyl and aryl ethers of polyhydric alcohol esters, polyethylene glycol fatty acid esters, aliphatic alkanolamides and polyoxyethylene aliphatic amides; fluorine surfactants such as MEGAFRCE manufactured by DIG Corporation,
EFTOL' manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd,, SURFLON manufactured by ASAHI GLASS CO,, LTD., Ftergent manufactured by WEOS COMPAWY LIMITED, UNIDYNE manufactured by DAIKIH INDUSTRIES, LTD., Fluorad manufactured 5 by Sumitomo 3M Limited, and Zonyl manufactured by Du Pont Kabushiki Kaisha; and silicon surfactants such as AQUALEN 8020, AQUALEN HS-01, AQUALKN SB-630, POLYFLOW KL-lOO, POLYFLOW KL-aOO and POLYFLOW WS-30 manufactured by KYOEISHA CHEMICAL CO., LTD. Of these, silicon surfactants are relatively 10 preferable. [00951
The amount of the surfactants added as reiguired is approximately in the range of 0.0001 to 20 wt%, preferably 0.001 to 10 wt%, and more preferably 0.01 to 5 wt^ relative to the 15 total of the compound (A) and the solvent. [0096]
The treatment liquid in the invention which contains the compound (A) may include, in addition to the compound (A) , the solvent and the surfactant {the leveling agent), various 20 organic compounds and inorganic compounds such as UV
polymerization initiators, radical fheat) polymejrization initiators, UV absoirbers, HASLS and fillers as long as the object of the invention can be achieved. [00971
The treatment liquid in the InvonLion which contains the compound (A) may be iipplied by various methods such as, for example, dip coating methods, pouring coating methods, spray coating methods, bar coating methods, gravure coating methods, 5 reverse roll coating methods, knife coating methods, kiss-roll coating methods and spin coating methods . The coating methods may bo soiccted appropriately in accordance with the configurations such as shapes of the films-[0098]
10 After the application, the solvent may be dried by various methods such as natural drying, air guns, fans, dryers and ovens Ovens Lond to bo suitably used. In the case of an oven, the dirying conditions may be such that the temperature is approximately in the range of 30 to 120'C and the drying time
15 is, foreKample, 1 minute to 10 hours, The drying of the solvent is not an essential step. For example, tho solvent may be dried simultaneously with the graft reaction, or the graft reaction may be performed without the drying of the solvent. [0099J
20 When the compound {A] is grafted to the acrylic resin gradient film by the application of radiations, electron beams or UV (ultraviolet) rays in the range of 200 to 400 nm are preferably used. The energy applied for tho graft reaction is approximately 100 to 5000 mJ/cm^.
[0100]
When the graft reaction is performed with heat, the coated film is heated at a temperature approximately in the range of 30 to 250''C for 0.1 to 24 hours. 5 [OIOIJ
After the graft reaction, the treated film (the acrylic resin modified film) is washed to remove the compound (A) that has not been involved in the graft reaction from the treated film {the acrylic resin modified film) . Highly polar solvents 10 such as water and alcohols may be preferably used. [0102]
By the graft treatment of the inventive acrylic resin gradient film with the compound (A) , the hydrophilicity of the acrylic resin gradient film may be further improved and the 15 antifogging properties may be enhanced. A small water contact angle (an impirovement in hydrophilicity) may be obtained approximately in the range of 1 to 30°. The surface of the modified acrylic; resin film treated with the compound (A) usually has a water contact angle of not more than 10", 20 preferably not more than 5", and more preferably not more than 4"- In general, surfaces such as mirrors in bathrooms or the likie easily become fogged. To prevent such fogging, the surface has to at least be rendered superhydrophilic such that the water contact angle is 5" or less and thereby the formation
of water droplets is suppressed (water is allowed to form a thin film). It is also required that the surface remain resistant to fogging for a long terra. [0103J 5 By virtue of the inventive hydrophillc t]:eatment
involving the grafting of the compound {A) to the acrylic resin hydrophilic film having a gradient of anionic hydrophilic groups, the formation of a water film is facilitated over a relatively long period of time. Thus, the inventive films are
10 useful for antifogging matej:iaJ.s and antifogging coating films (or antifogging coats) requiring high antifogging properties. Further, the inventive modified acrylic resin films probably have high antistatic performance and tend to exhibit excellent scratch resistance.
15 [0104]
The highly hydrophilic modified acrylic resin films obtained by the present invention may be stacked onto various substrates such as PET, PC, PMMA and glass. For example, hydrophilic film stacks including the inventive coating films
20 may be used as antifogging films or the like that can be readily attached to surfaces such as glasses, mirrors in fogging environments such as lavatories and bathrooms, screens such as displays and televisions, information boards such as signboards, advertisements and guideboards, indicators such
as railroad indicators and traffic signs, exterior walls and
interior walls of buildingH, and window glasses.
[0105]
Because of oKcellent hydrophilicity, the modified 5 acrylic resin films obtained by the invention are also useful in other applications such as antifogging materials, antifouling materials, anti-condensation materials, anti-water droplet materials and antistatic materials, For example, the inventive films may be used in applications
10 including materials for transport machines, typically
automobiles, ships and airplanes, such as bodies, wheels, exterior materials and interior materials; building materials and housing materials such as exterior wall materials, interior wall materials, floor materials, furniture materials, bathroom
15 materials, lavatory materials, kitchen materials such ss air fans, toilet materials, and inner surface and outer surface materials for pipes; construction materials such as sound insulating boards located on roads such as expressways; garment materials such as cloths, fabrics 3.nd fibers; optical materials
20 such as windows, mirrors, optical films, optical disks,
eyeglasses, contact lenses, goggles, reflective films and reflectors; illuminating materials such as lamps and lights; industrial materials such as cooling fins; electric and electronic materials such as electric appliance materials,
wiring materials, materials for displays such as touch panels and flat panels, and photoresists ; printing base materials such as inkijet recording plates, and printing or typing primers; commodity materials such as cosmetic containers; and dental 5 materials such as dentures. [0106]
From the foregoing, the present invention resides in the following.
[1] 10 A modified acrylic jresin film obtained by treating a surface of an acrylic resin film having anionic hydrophilic groups with a compound [A) , the acrylic resin film being such that the concentration of the anionic hydrophilic groups on the surface is higher than the concentration of the anionic 15 hydrophilic groups at a depth half the film thiclcness from the surface of the acrylic resin film, the compound (A) having in the molecule thereof one or more anionic hydrophilic groups and one or more groups selected from groups having a polymerizable carbon-carbon double bond, amino groups, 20 mercapto groups and hydroxyl groups. [2]
The modified acrylic resin film described in [1], wherein the treatment is graft treatment. [3]
The modified acrylic resin film described in [1] or [2] , wherein the compound [h] is one or more selected from compounds represented by General Formulae (1) to (5):
General Formula £1}
[01071
Chem. 16]
O
(1)
[0108]
fin Formula (1), Dl is a (meth) acryloyloxy group (only
10 when q is 1) , a (meth) acryloylthio group {only when q is 1) , a {methjacrylamide group (only when q is 1), a vinyl group, an allyl group, an isopropenyl group, a styryl groups a mercapto group, an amino group, a methylamino group or an cthylamino group; Z is a hydrogen ion, B,n ammonium ion, an ainine ion, an
15 alkali metal ion or an alkaline earth metal (1/2 atom) ion; R is a divalent aliphatic hydrocarbon group having 1 to 600 carbon atoms and may include one or more groups selected from aromatic rings, alicyclic groups, ether groups and ester groups; and q is 0 or 1),
20 General Formula (2)
[0109] [Chem. 17]
o
w o
O 1 \ ^nr
R,
(2)
[0110]
(in Formula (2), R^ and Rs represent a hydrogen atom or
a methyl group; R-? represents a hydrogen atom or an alkyl group
5 having 1 to 6 carbon atoms; Z is a hydrogen ion, an ammonium
ion, an amine ion, an alkali metal ion or an alkaline earth
metal (1/2 atom) ion; and nl is an integer of 1 to 10),
General Formula (3) [OlllJ 10 [Chem. 18]
^ (3)
[0112]
(in Formula (3), Dl is a (meth) acryloyloxy group (only
when q is 1), a (meth) acryloylthio group (only when q is 1),
15 a (meth)acrylamide group (only when q is 1), a vinyl group,
an allyl group, an isopropenyl group, a styryl group, a mercapto
group, an amino group, a methylamino group or an ethylamino
group; Z is a hydrogen ion, an aitimoniuiti ion, an amine ion, an alkali metal ion or an alkaline earth metal fl/2 atom) ion; R is a divalent aliphatic hydrocarbon group having 1 to 600 carbon atoms and may include one or more groups selected from aromatic rings, aiicyclic groups, ether groups and ester groups; and q is 0 or 1), General Formula (4j [0113] [Chem. 191
10
D2
-R —oj P-^O-Z
b
(4)
[0114
15
20
fin Formula (4), D? is a (meth)acryloyloxy group, a fmeth)acryloylthio group, a (meth)acrylamide group, a vinyl group, an allyl group, an isopropenyl group, a styryl group, a mercapto group, an amino group, a methylamino group or an ethylamino group; Z is a hydrogen ion, an ammonium ion, an amine ion, an alkali metal ion or an allcaline oarth metal fl/2 atom) ion; R is a divalent aliphatic hydrocarbon group having 1 to 600 carbon atoms and may include one or more groups selected from aromatic rings, aiicyclic groups, ether groups and ester groups; a and b represent integers of 1 or 2, and a + b = 3; when a is 2, D^s or Rs may be the same or different from each other; and when b is 2, Zs may be the same or different from
each other),
General Formula (5
[0115] rchem. 20
(S)
0116]
[in Formula (5), D3, R3 and 3O3S are groups bonded to carbon atoms on the ring(s) in the above formula; D3 independently at each occurrence represents a vinyl group, an allyl group, an
10 iaopropenyl group, a styryl group, a mercapto group, an amino group, a methylamino group, an ethylartiino group or a hydroxyl group; Z is a hydrogen ion, an ammonium ion, an amine ion, BLU alkali metal ion or an alkaline earth metal {1/2 atom) ion; R3 independently at each occurrence represents H, a methyl group,
15 an ethyl group, a methoxy group, an ethoxy group, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; k is an integer of 0 to 10; 1 and m indopendently represent an integer of 1 to 11; k + l+nL=2to6-i- 2n; n is an integer of 0 to 3; when 1 is 2 or greater, D3S may be the same or different from
20 each other; when k is 2 or greater, R35 may be the same or different from each other; and when m is 2 or greater, Zs may be the same or different from each other), and
General Formula {6}
0117J
Chem. 21
(6)
5 [OllBJ
[in Formula (6) , D3, R3 and SO3S are groups bonded to carbon atoms on the ringts) in the above formula; D3 independently at each occurrence reprosenta a vinyl group, an allyl group, an isopropenyl group, a styryl group, a mercapto group, an amino
10 group, a methylamino group, nn ethylamino group or a hydroxyl group; S is a hydrogen ion, an ammonium ion, an amine ion, an alkali metal ion or an alkaline earth metal {1/2 atom) ion; R3 independently at each occurrence represents H, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a fluorine
15 atom, a clilorine atom, a bromine atom or an iodine atom; r is an integer of 0 to 6; q and p independently represent an integer of 1 to 7/ p + q -^ r ^ 2 to 8; when p is 2 or greater, Dss may be the same or different from each other; when r is ;^ or greater, R3S may be the same or different from each other; and when q
20 is 2 or greater, Zs may be the same or different from each otherj ,
The modified acrylic resin film described in [3] , wherein
the compounds represented by General Formula (1) are compounds
represented by General Formula f7):
[0119]
[Chem. 22]
b
(7)
[0120]
(in Formula (7), Dl is a £meth j acryioyloxy group [when any of x and y is 1 or greater), a (meth)acryloylthio group {when any of K and y is 1 or greater) , a (meth) acrylamide group 10 (when any of x and y is 1 or greater) , a vinyl group, an allyl group, an isopropenyl group, a styryl group, a mercapto group, an amino group, a methylam.ino group or an ethyiamino group;
5 is a hydrogen ion, an ammonium ion, an amine ion, an alkali
metal ion or an alkaline earth metal (1/2 atom) ion; Ri to R4
15 are independently a hydrogen atom, an alkyl group having 1 to
6 carbon atoms or an alkozy group having 1 to G carbon atoms;
V and y are independently an integer of 0 to 10; w is 0 or 1
(when any of v and y is 0, w is 0); x is an integer of 0 to 10; when v is 2 or greater, Rjs or R2S may be the same or different 20 from each other; when y is 2 or greater, R33 or R4S may be the same or different from each other; and when x is 2 or greater, RLS or R2S may be the same or different from each other) .
[5]
A stack including a aubatrate and the modified acrylic resin film described in any of [I] to [A]. [6] 5 A method for producing modified acrylic resin films, including treating a surface of an acrylic resin film having anionic hydrophilic groups with a compound [h], the acrylic resin film being such that the concentration of the anionic hydrophilic groups on the surface is higher than the 10 concentration of the anionic hydrophilic groups at a depth half the film thickness from the surface of the acrylic resin film, the compound (ft) having in the molecule thereof one or more anionic hydrophilic groups and one or more groups selected from groups having a polymerizable carbon-carbon double bond, amino 15 groups, mercapto groups and hydroxyl groups. [7]
The method for producing modified acrylic resin films described in (61 , including a step of forming the acrylic resin film on a substrate. 20 [8]
The method for producing modified acrylic resin films described in [7], wherein the acrylic resin film is such that the concentration of the anionic hydrophilic groups on the side of the surface opposite to the side adjacent to the substrate
X3 higher than tho concentration of the anionic hydrophilic
groups at a depth half the film thickmess from the surface of
the acrylic resin film.
[01211 5 [EXfiMPLESj
The present invention, will be described in greater detail
by presenting examples hereinbelow without limiting the scope
of the invention to such examples.
[012:?] 10 In the invention, properties of coating films were
evaluated in the following manner.
[0123]
(Measurement of degree of polymerization of acrylic resin films
fresin films to be subjected to graft treatment)) 15 An acrylic resin coating liquid was applied to a substrate,
and a solvent was dried off. The intensity of the >C=CH2 peak
at 808 cm~* (a base line method) was measured before and after
UV irradiation, and the polymerization degree was calculated
from the following equation. 20 [0124J
Polymerization degree (mol%) = (pealc intensity before UV
irradiation - peak intensity after UV irradiation)/peak
intensity before UV irradiation x 100
(Measurement of anion and cation concentration ratio)
A sample was cut at a slant as illustrated in the view
of sample preparation in. Fig. 1. Tho anion concentration [Sa)
in the outer surface and the anion concentration tDa) at the
middle point were measured with a time-of-f light secondary .Ion
5 mass spectrometer (TOF-SIMS). The obtained values were
expressed as an anion concentration ratio (Sa/Da) of the anion concentration in the outer surface of the film in contact with the outside air to the anion concentration at the middle point between the inner surface and the outer surface of the film. 10 Eftnalyzer and measurement conditions)
TOF-SIMS: T0F-SIMS5 manufactured by ION TOP Primary ions: Bi32"^ (accelerating voltage 25 kV) Measurement area: 400 ^m^
In the measurement, a neutralizing gun for correcting 15 electric charges was used.
(Preparation and analysis of sample)
As illustrated in Fig. 1, a sample in which a coating layer 20 was disposed on a surface of a substrate 10 was cut at a slant accurately along a cutting direction 30. Thereafter, an 20 approximately 10 x 10 mm^ piece was cut out, and a mesh was placed on the measurement surface. The sample was then fixed to a sample holder, and the anion concentrations were measured with a time-of-flight secondary ion mass spectrometer (T0F-SI>3S) with respect to a coating layer surface 40 in contact with the
outside air and an innei: portion 50 of the coating layer which was inside of the film (at a point half (i/2) the film thickness, a surface of the inside of the coating layei: in contact with the substirate IQ) . 5 (Evaluation)
The evaluation was made according to the equation below. The ion concentrations at the measurement points were based on relative intensities {relative to the total of the detected ions).
10 [01251
Sa/Da (anion concentration ratio, degree of gradient) = anion concentration at coating layer surface 40/anion concentration at 1/2 film thickness of coating layer 20 (Measurement of water contact angle)
15 The water contact angle was measured with respect to 3 points for each sample by use of water contact angle meter CA-V manufactured by Kyowa Interface Science Co . , Ltd. The measured values were averaged to give a value of water contact angle. [0126]
20 (Measurement of haze)
The haze was measured with respect to 4 points for each sample by use of haze meter NDH2000 manufactured by NIPPON DCNSHOKU INDUSTRIES CO,, LTD. The measured values were averaged to give a haze value.
[0127J
(Evaluation of adhesion)
The adhesion was evaluated by a crosscut adhesion test. [01281 5 (Evaluation of antifoviling properties)
The surface was marked with oil-based markef "Hackee Gokuboso (ultrafine)" (black, coder MO-12 0-MC--BK) manufactured by ZEBRA CO. , LTD ., and water droplets were dropped thereon, allowed to stand for 30 seconds, and wiped with tissue 10 paper. The antifoulitig properties were evaluated to be O when the mark came off, and x when the mark did not come off and remained, [0129]
(Evaluation of resistance to breath fogging) 15 The resistance to breath fogging was evaluated to be O when the surface did not become fogged with breath, and x when the surface became fogged with breath. [0130]
(Evaluation of antifogging properties with AFA-1) 20 An antifogging property evaluation device [antifog
analyEer "AFA-1" manufactured by Kyowa Interface Science Co., Ltd.) was used in the measurement. The antifogging properties were evaluated to be O when all the antifogging indexes obtained during the measurernent were 2 or below, and were evaluated to
be X when the antifogging index exceeded 2 at least one time,
Conditions in measurement with AFA-1
Water vapor teraperaturei SS^C
Measurement room temperature: 16"C
5 Measurement method: Antifogging index was measured at
time intervals of 3 seconds. The sample was allowed to stand
from the start, namely^ from 0 second until 15 seconds. -> The
35"C watei: vapor was continuously sprayed from 15 seconds until
1 minute 15 seconds. -> The spraying of water vapor was stopped 10 and the sample was forcibly dried from 1 minute 15 seconds until
2 minutes 15 seconds.
[Production Example 1] Production of coating surface
fhydrophilic film) having anionic hydrophilic groups]
(Preparation of coating solution 1) 15 According to the formulation shown in Table 1, a
homogeneous coating liquid 1 having a solid content of 55 wt% was prepared.
[0131]
[Table X] Table 1 Goatiny liquid 1
Component5 Amounts {gj Concentrations fvft^)
SPA-K 0.35 1.0%
P-2M 0.09 0.2%
A-GLY-yR 5.86 1&,5^
A9300-1CL 0.98 2.6%
U-15HA 12.TO 35.7%
Methanol 12.00 33.7^
Acetone 3.00 8.4%
S-F.KD 0.02 0.1%
Darof^ur 1173 0.60 1.7^
35.60 100.0%
Solid content [wt%) ^ 57%
roi3?i
[Chem. 23 J
n>
SPA-K 232.30
o-p-o o
P-2M 322-25
V
o
I
S A-GLY-9E A. 650.71
O
{To
o
'^UyO
^^Acr^N^N^^5C^.^.O^
O
A-9300-ia. 537.20
S-EED 442.64
Darociirl 173 164.20
[0133
(Measurement of solubility in cyclohexane;toluene = 5:1 (by 5 weight))
To a mixed solution weighing 10.0 g which contained 8.3
g of cyclohexane and 1.7 g of toluene, 1.0 g of SPA-K {3-sulfopropyl aorylate potassium salt, a hydrophilic compound for forming a gradient film according to the invention) was added. The mixture was stirred at 25''C for 1 hour and was 5 filtered through a 0.45 \im meinbrane filter. [013^]
The filtrate was added to an evaporating dish and was dried by being heated at 150°C for 2 hours. The residue was cooled to room temperature and the weight thereof was measured. 10 [0135]
Lastly, the solubility in cyclohexane;toluene = 5:1 (by weight) was obtained according to the equation below. [0136]
Solubility (wt%) = mass of residue (g)/{10.0 (g) + mass
15 of residue (g)) x 100
The solubility was found to be less than 1 wt%.
(Formation of films (gradient films) having concentration of
anionic hydrophilic groups higher on the surface than at depth
(inside) half the film thickness from the surface)
20 The coating solution 1 was applied onto a polycarbonate
sheet (hereinafter, referred to as PC sheet) as a substrate with a bar coater No, 6 at room temperature (26°C-20% RH) . The coating was allowed to stand (dry) for 1 minute and was passed one time through a UV conveyer (manufactured by Fusion tiV
Systems, Japan, an electrodeless discharge lamp, H valve, output 50%, conveyer speed 30 m/min) [accumulated dose 90 mj/cm^) , thereby forming a gradient film with a film thickness
of approximately 5 jim on the PC sheet. In the coating film, 5 the degree of polymerization of acrylic groups was 50 mol%. Property measurements and TOF-SIMS anEilysis were performed. The results are shown in Table 2,
[0137]
[Table 2]
Table 2
RcBulta of analysis of coating film in J^rprfiiotioil Fxaniple 1
Relative intensity of sulfonic qcoups on film sudTiSCe- S-J (^)
SO^" {Di/z aO) 4 ■ St
Relative intensity of sulfonic cfroups in middle portion of film, Sb (SJ
ao^' (in/a aO) 2.31
portion 2.0
Docfree of uneven distribution fgrjidient) of. aulfouio groups in film .■iO^" on film !iurf.ioc/:;o*" in middle portion
10 [0138]
[Example 1]
First, a treatment liquid for the graft treatment of a surface of the film produced in Production Example 1 was prepared according to the formulation described in Table 3. 15 [0139]
[Table 3]
Table 3 Graft treatment liquid ^_
Amoun ts (g)
5. 00
50 .00
bO .00
0. 15
105 i,15
5, 0%
Components
Compound with anionic hydrophilic groups: SPA-K
Water
BGM: ethylene glycol monontethyl ether
Surfactant: POLYFLOW KLIOO manufactured by KYOEISHA
CHEMICAL CO., LTD.
Total
Solid content NV fwt%) ^
[0140J
The graft treatment liquid wag applied onto a surface of the coating film produced in Production Example 1 with a bar coater No. 20 and was hot air dried at 40 to 50"C for 2 to 3 minutes. Thereafter, the film was passed one timo through a 5 UV conveyer (manufactured by Fusion UV Systems, Japan, an electrodelesa discharge lamp, H valve, output 100%, conveyer speed 6 m/min) (accumulated dose 900 mJ/cm^) ; thereby performing the graft treatment on the surface of the coating filin and completely curing the film. Lastly, tho surface of
10 the film obtained was washed with running water while lightly rubbing the surface with a polyurethane sponge. The film was then dried with a hot air dryer and was cooled to room temperature, thereby giving a coat. The results are shown in Table 6.
15 [0141]
[Comparative Example 1j
The test was performed in the same manner as in lixample 1, except that the graft treatment liquid was not applied. The results are shown in Table G,
20 [0142J
[Comparative Example 2j Graft treatment test 1 with respect to films without changes (gradient) of concentiratlons of anionic hydrophilic groups between on the surface and at depth (inside) half the film thickness from the surface
Reference: JP-ft-2001-98007, Kawamura Institute of Chemical
Research
(List of compounds used)
"M-114": nonylphenoxypolyethylene glycol (n = 8) 5 acrylate {"M-114" manufactured by TOAGOSEI CO., LTD., HLB value: 11.25J
"V-^263": trifunctional urethane acrylate oligomer
having an average molecular weight of approximately 2000
("UNIDIC V-4263" manufactured by DIG Corporation^
10 "HDDA": 1,6-hexanediol diacryiate ("NEW FRONTIER HDDA"
manufactured by DAI-ICHI KOGYO SEIYAKU CO., LTD,j
"HR200": 2-methacryloyloKyethyi acid phosphate ("MR200" manufactured by DAIHACHI CHEMICAL INDUSTRY CO., LTD.)
"PMNElO": polyethylene glycol mono-4-nonyl phenyl ether 15 (n' = 10) ("polyethylene glycol mono-4-nonyl phenyl ether (n' = 10)" manufactured by Tokyo Chemical Industry Co., Ltd.)
"Irg. 184": l-hydroxycyclohexyl phenyl ketone f'lRGACURE 18 4" manufactured by Ciba-Geigy) {Preparation of coating liquid) 20 A coating liquid was prepared by mixing 20 parts of
"V-4263" and 20 parts of "HDDA" as crosslinkable polymerizable compounds, 60 parts of "M114" as a polymerizable compound, and 5 parts of "Irg. 184" as a photopolymerisation initiator. [Preparation of graft treatment liquid)
A solution as a hydrophilic layer-forming material was
prepared by mixing 5 parts of "PMNElO", 5 parts of "MR200" as
a hydrophilic compound, and 90 parts of water.
(Fabrication, of coating film to be graft treated) 5 The coating liquid was applied onto a 7. mm thick PC sheet
with a bar coater and was irradiated with UV rays to 200 mJ/cm^
(accumulated doae) with use of the UV illuminator described
in Example 1. Thus, a film was formed on the PC sheet.
[0143] 10 In this film, the degree of polymerization of acrylic
groups was 60 mol%.
(Graft treatment)
Next, the stack of the PC sheet and the film was placed
in the graft treatment liquid prepared above for 1 minute, and 15 was lifted. Thereafter, the stack was irradiated with UV rays
to 1500 mJ/cm^ (accumulated dose) and thereby the film was
completely cured.
[0144]
The film obtained was washed with running water, dried 20 with a hot air dryer, and cooled to room temperature, thereby
giving a coat. Tlie results are shown in Table 6.
[0145]
[Comparative Example 3] Graft treatment test 2 with respect
to films without changes (gradient) of concentrations of
anionic hydrophilic groups between on the surface and at depth
(inside) half the film thickiness from the snrfaco
Reference: JP-ft-2011-229734, Sekisui Hometechna Co., Ltd.
(Preparation of coating liguid)
A coating liquid was prepared according to the
formulation shown in Table 4 below.
[0146]
{Table 4]
Table 4 Composition of ooatirtg liquid
NOH, Coioponents Amounts
(g) Concn-(wt%J
1 OligorasE U-15IIA. manufactured by SHItf-NAKfiMURA CHEMICAL CO.. LTD. G.O 24.4*
2 Hoiiomer Pontaccythritol triacrvlate 2.0 e.ll
3 Phot opol yiac r i z at ion iljiLiatOC (iRGACUKlii 127) 2-llyEodKy-l-'{4-|4-(2"hvdroxy-2-'
inathyl-propionyl)-benzyl}phenyl } - 2-ine i:hy 1 - p ropa n-1 - oiiQ 0.4 1.2%
4 So]vent-1 Methyl flthyl ketone IB. 0 54.9%
5 Solvem:-2 Ethyl acetate 1.3 4.U%
fi ^olvent-3 Toluene 3.1 ^.b*
32. e
32%
100.0%
To Lai
^lOlid content =
10 [01471
(Fabrication of coating film)
The above primer coating liquid was applied onto a PC sheet aa a substrate with a spray gun while the dry film thickness was designed to be 12 \im (as dry) . The wet film was dried by
15 being allowed to stand at room temperature for 3 minutes and in a hot air dryer at SC'C for 3 minutes. In the same manner as in Example 1, the film was UV .irradiated (lamp output 50^, conveyer speed 30 m/min, accumulated dose 90 mJ/cin^) , thereby giving a coating film on the PC sheet.
20 In the film, the degree of polymerization of acrylic
groups was 50 mol%.
(Preparation of graft treatment liquid)
A graft tireatment liquid was prepared according to the formulation shown in Table 5 below.
[01481
Amount;
ConcTi. (wtl)
[Table 5] Table 5
Hos.
Compononts
Hydrophilic inDnoiiii^r
ATUS;
in.o
21.6%
2-Eirirylanijdo-?-roethylpropanesQlfonic at:!d majiufactured by TOAGOStll CO,, LTD
Alkali SQlvont-1 Solvent-2
S. 6%
2.6
Sodium carbonate
12, fi
?.1.2%
22 . fi 2^^
ion ^xclkEjn^^ wster
^e.Bi
Ethanol
]00.0^
Total
Solid content =
[0149]
(Graft treatment) 10 In the same manner as in Example 1, the surface of the coating film on the PC sheet was treated with the graft treatment liquid described in Table 5, thereby giving a coat. The results are shown in Table 6.
[0150
Rppeacance ^atec contact angle Ha^e
[Table 61 Table e
tJ5£-
EK- 1 Tra^-sparent
Comp, EK. 1 TraT.aparsnt
Camp. Ex. 2 Tiarisjjatent
Ccmp. Ex. 3 Slightly whitQ
Psdhesion Hntifouling properties ant
o
o
B
3 0.2 100/100
5 0.2 100/100
A4 0.5 0/100
34 2.3 0/103
[0151]
[Reference Example 1] Test with coating liquid 1 without anionic hydrophilic monomers
The test was performed in the same manner as in Example 1, except that the coating solution 1 described in Table 1 was replaced by a coating solution 2 described in Table 7. (The degree of polymerization of acrylic groups in the film before the graft treatment was SO mol%.)
[01521
The stack of tho graft treated film on the PC sheet was soaked in hot water at SO^C to evaluate hot water resistance. The result is shown in Table 8, together with the results obtained with the stacks of Example 1 and Comparative Example 1.
[0153]
[Table 7]
Table V Coating liquid 2
COTtiponetits
SPA-K P-2M
A-GLY-9E
A9300-1CL
U-ISHA
Methanol
Acetone
S-EED
Darocur 1173
Solid content (wf
[0154J
Amounts (g)
5.B6
0.98 12.70 12.00
3.00 0.02 0,60
35,16
Concentrations jwt%)
0, 0^
0. 0^
16 .7%
2. 3%
36 .1%
34 .1%
B. 5%
0. 1%
1. 7%
lOf ).0%
57%
The films obtained in Example 1, Comparative Example 1
and Reference Example 1 were soalced in hot water at 90"^ for J. day, 4 days, 9 days or 14 days, and the water contact angle and the haze were measured. The results are shown in Table 8, [0155] [Table B]
N03, Duration o£ 0 day 1 day
3 4 0.2 0.2 soaking in hot 4 days
4 0.2 water at 90 9 days
4 0. 3 14 days
4
0. 3 Remarks
EK. 1
Gradient + grafting
COIiip.
E::- 1 5 0.2 5 0.2 7 0.2 8 0.3 11 0.3 (Gradient .-jlone
ReE. EK. 1 5 0.2 5 0.2 e
0.2 22 0.3 30 0. 3 Grafting alone
Upper viiluesi water contact angle Lower valuer: haze
[0156]
[Examples 2 to 17]
The test was performed in the same manner as in Example 1, except that the anionic hydrophilic compound [the grafting compound) in the graft treatment liquid described in Table 3 was changed. The results aro shown in Table 9.
[0157]
(Table 9-1]
M Ol
th
1"
o
-H
u
O
O
O
O
O
O
O
O
O
O
a
I'
u f) P-
c u
if■H
13
O
SI -H
o
o
o
o
o
o
o
o
u --I
□ n
-H
<-l
E:
]l
EH
nJ U
E'
El
E'
□ 01 ll n| P.
□
n|
El f
m a
a
VI
'J
E-i
-u u
1
»
I! ra
El
H
i:
u p.
c
m u
I-
l.o
=o
o..
z
^
^=^
'D
xz
•!0
I
14 u
S
or
-rt
4J Er
i!f
n. o
ki
0.
i^ "I
□L
o
O
o
O
O
O
O
O
OI
-I |i
1-1
a □
14 (J.
Di
El FH
□
O
O
O
O
IT)
oi
V
M
" f t 4J u |J
c ti □ m C c
Ql 91 01 cj ip m
H CO .-[
{M IT, Si
1 iH r-H
tM J3
1 £0
Ti- tH
to '—'
O '
' pa
•u
^v
<
>^ o..^ 0=,° 'v:
^
»s
i ^i ss
Reference Signs List
0161]
10: SUBSTRATE
20
COATING LAYER
5
30
CUTTING DIRECTION
40
COATING LAYER SURFACE
50
iHSlDf; Olr^ COATING LAYER
WE CLAIMS:-
1. A modified acrylic resin film obtained by treating a surface of an acrylic resin film having anionic hydrophilic 5 groups with a compound (A), the acrylic resin film being such that the concentration of the anionic hydrophilic groups on the surface is higher than the concentration of the anionic hydrophilic groups at a depth half the film thickness from the surface of the acrylic resin film, the compound (A) having in 10 the molecule thereof one or more anionic hydrophilic groups and one or more groups selected from groups having a polymerizable carbon^carbon double bond, amino groups, mercapto groups and hydroxyl groups.
15 2. The modified acrylic resin film according to claim
1, wherein the treatment is graft treatment.
3, The modified acrylic resin film according to claim 1 or 2, wherein the compound fA) is one or more selected from 20 compounds represented by General Formulae (1) to (6): General Formula (1) [Chem. 1]
\ O
o.-{nU-o-
•i (1)
(in Formula (1), Di is a fme1:h) acryloyloxy group (only when q is 1), a (meth) acryloylthio group fonly when q is 1), a (meth)acrylamide group (only when q is 1], a vinyl group, 5 3.n allyl group, an Isopropenyl group, a styryl group, a mercapto group, an amino group, a methylamino group or an ethylamino group; Z is a hydrogen ion, an ammonium ion, an amine ion, an alkali metal ion or an alkaline ea]:th metal (1/2 atom) ion; R 13 a divalent aliphatic hydrocarbon group having 1 to 600 10 carbon atoms and may include one or more groups selected from aromatic rings, alicyclic groups, ether groups and ester groups; and q is 0 or 1), General Formula (2) [Chem. 2]
0
w
0
o 1 ^ 'nr
15
R,
5 <2)
(in Formula (2), R^ and R^ represent a hydrogen atom or a methyl group; R7 represents a hydrogen atom or an alkyX group
having 1 to 6 carbon atoms; Z is a hydirogen ion, an ammonium ion, an amine ion, an alkali metal ion or an allcaline earth metal (1/2 atom) ion; and nl is an integer of 1 to 10), General Formula {3) 5 [Chem. 3]
Di-hR-
'C-0—2
II
O
(3)
10
15
fin Formula [3), D^ is a (meth)acryloyloxy group (only when q is 1), a (meth) acryloylthio group (only when q is 1) , a (meth)acrylamide group (only when q is 1), a vinyl group, an allyl group, an isopropenyl group, a styryl group, a mercapto group, an amino group, a methylamino group or an ethylamino group; 7. is a hydrogen ion, cin ammonium ion, an amine ion, an alkali metal ion or an alkaline earth metal (1/2 atom) ion; R is a divalent aliphatic hydrocarbon giroup having 1 to 600 carbon atoms and may include one or more groups selected from aromatic rings, alicyclic groups, ether groups and ester groups; and q is 0 or 1), General Formula (4) [Chem. 4J
20
D2-R—O-^ P+O—Z
b
(4)
(in Formula (4), D? is a (meth)acryloyloxy group, a
10
fmeth)acryloylthio group, a (meth)acrylamide group, a vinyl group, an allyl group, an isopropenyl group, a styryl group, a mercapto group, an amino group, a methylamino group or an ethylamino group; Z is a hydrogen ion, an aminoniuni ion, an amine ion, an alltali motal ion or an alkaline earth metal fl/2 atom) ion; R is a divalent aliphatic hydrocarbon group having 1 to 600 carbon atoms and may include one or more groups selected from aromatic rings, alicyclic groups, ether groups and eater groups; a and b represent integers of 1 or 2, and ^ + b = 3; when a is 2, D2S or Rs may be the same or different from each other; and when b is 2, Zs may be the same or different from each other),
General Formula (5)
iChem. 51
15
20
(D3) I- -
(5) fin Formula (5) , Dj, R3 and SOgZ are groups bonded to carbon
atoms on the ring(s) in the above formula; D3 independently at
each occurrence represents a vinyl group, an allyl group, an
isopropenyl group, a styryl group, a mercapto group, an amino
group, a methylamino group, an ethylamino group or a hydroxyl
group; Z is a hydrogen ion, an ammonium ion, s.n amine ion, an
alkali metal ion or an alkaline earth metal (1/2 atom) ion;
Rj independently at oach occurrence represents H, a methyl group, an ethyl group, a metJioxy group, an ethosy group, a fluorine atoin, a chlorine atom, a bromine atom or an iodine atom; k is an integer of 0 to 10; 1 andm independently represent an integer 5 of 1 to 11; k t 1 + m = 2 to 6 + 2n; n ia an integer of 0 to 3; when 1 is 2 or greater, Djs may be the same or different from each other; when k is 2 or greater, R^s may be the same or different from each other; and when m is 2 or greater, Zs may be the same or different from each other), and 10 General Formula (6) [Chem. 6]
(6) fin Formula (6) , Dj, Rg and SO3S are groups bonded to carbon
atoms on the ringfs} in the above formula; Dg independently at
15 each occurrence represents a vinyl group, an allyl group, an
isopropenyl group, a styryl group, a mercapto group, an amino
group, a methylamino group, an ethylamino group or a hydroxyl
group; S is a hydrogen ion, an ammonium ion, an amine ion, an
alkali metal ion or an alkaline earth metal (1/2 atom) ion;
20 R3 independently at each occurrence represents H, a methyl group,
an ethyl group, a methoxy group, an ethoKy group, a fluorine
atom, a chlorine atom, a bromine atom or an iodine atom; r is
an integer of 0 to 6; q and p independently represent an integer of 1 to 7; p + q + r = 2 to 8; when p is 2 or greater, D33 may be the same or different from each other; when r is 2 or greater, R3S may be the same or different from each other; and when q 5 is 2 or greater, Ks maybe the same or different from each other) .
4, The niodifted acrylic resin film according to claim 3, wherein the compounds represented by General Formula (1) are compounds represented by General Formula (7):
10 [Chem. 7]
(7)
{in Formula (7), Di is a (meth)acryloyloxy group (when any of x and y is 1 or greater), a (meth)acryloylthio group (when any of x and y is 1 or greater) , a (meth) acrylamide group
15 (when any of x and y is 1 or greater) , a vinyl group, an allyl group, an isopropenyl group, a styryl group, a mercapto group, an amino group, a methylamino group or 3.n ethylamino group; Z is a hydrogen ion, an ammonium ion, an amine ion, an alkali metal ion or an alkaline earth metal (1/2 atom) ion; Ri to R4
20 are independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 6 carbon atoms; V and y are independently an integer of 0 to 10; w is 0 or 1
{when any of v and y is 0, w is 0); x is an integer of 0 to 10; when v is 2 or greater, RIB or R?s may be the same or different from each other; when y is 2 or greater, R3S or R^s may be the same or different from each other; and v/hen x is 2 or greater, 5 Ris or R2S may be the same or different from oach other).
5, A stack comprising a substrate and the modified acrylic resin film described in any of claims 1 to 4.
10 6. A method for producing modified acrylic resin films, comprising treating a surface of an acrylic resin film having anionic hydrophiiic groups with a compound (R), the acrylic resin film being such that the concentration of the anionic hydrophiiic groups on the surface is higher than the
IS concentration of the anionic hydrophiiic groups at a depth half the film thickness from the surface of the acrylic resin film, the compound [A) having in the molecule thereof one or more anionic hydrophiiic groups and one or more groups selected from groups having a polymerizable carbon-carbon double bond, amino
20 g):oup3, mercapto groups and hydroxyl groups.
7. The method for producing modified acrylic resin films according to claim 6, comprising a step of forming the acrylic resin film on a substrate.
R. The method for prodvicnng modified acryJ ic resin
filiTLS acc^ording to claim 7, vjtierein Lhe acrylic resin lilm 13 such that the concentraLion of the anionic hydrophilic groups b on the j^ide of Lhci surface opposiL(5. to the sidO adjacent to the subsLratts is higher Lhan the ooncenLration of the anionic hydrophi lii^ groups at a depth half the fi Im thick-H<^ss troiri the surface of the acrylic rosin f.i Im.