CN107107543A

CN107107543A - Matrix with anti-soil film

Info

Publication number: CN107107543A
Application number: CN201580058199.6A
Authority: CN
Inventors: 藤井健辅; 宫村贤郎; 桥本匡平
Original assignee: Asahi Glass Co Ltd
Current assignee: AGC Inc
Priority date: 2014-10-30
Filing date: 2015-10-27
Publication date: 2017-08-29
Anticipated expiration: 2035-10-27
Also published as: JPWO2016068112A1; KR20170076660A; WO2016068112A1; TW201621001A; KR102378656B1; CN107107543B; JP6642444B2; TWI675077B

Abstract

The present invention provides a kind of matrix with anti-soil film; it is to possess anti-soil film, adhesive layer and diaphragm and the matrix with anti-soil film that the adhesive layer and the diaphragm are removed and used successively in the interarea of transparent base; the blooming for possessing the anti-soil film in the state of the adhesive layer and the diaphragm is 10nm~50nm, and the blooming for removing the anti-soil film after the adhesive layer and the diaphragm is 3nm~30nm.

Description

Matrix with anti-soil film

Technical field

The present invention relates to a kind of matrix with anti-soil film.

Background technology

Touch panel used in smart mobile phone, tablet personal computer, automobile navigation apparatus etc. due to contacting people when in use Finger, therefore, easily adhere to the dirt brought by fingerprint, sebum, sweat etc..If moreover, these dirts adhere to, being difficult to take off Fall, the part of dirt attachment is different from part that dirt is unattached more obvious according to the scattering of light, the different of reflection.Cause This, be attached with these dirts touch panel exist infringement observability, it is attractive in appearance such the problem of.And then, in display glass, light Learn the problem of having also indicated that same in element, sanitary equipment etc..

The problem of in order to eliminate such, it is known that the part contacted in the finger of these parts, the people of equipment is using being formed with The method of the matrix for the anti-soil film being made up of fluorine-containing water-disintegrable silicon compound.For forming the anti-soil film on matrix, in order to press down Dirt attachment processed, it is desirable to high water repellency and oil repellent, and require the wear resistance of the wiping to adhering to dirt.

As the above-mentioned anti-soil film with water repellency and oil repellent, for example Patent Document 1 discloses use fluorine-containing oxygen The polymer modification silane of alkylidene and the 9 of the polymer of fluorine-containing oxyalkylene:Solidify envelope and band formed by 1 mixture Solidify the glass basis of envelope.In addition, Patent Document 2 discloses will constitute the fluorine-containing dry type constituted painting using by specific The fluorine-containing dry coating agent that cloth agent is diluted with diluent carries out the glass basis with anti-soil film of dry type coating.

When being conveyed after the manufacture glass basis as described above with anti-soil film, for the glass of anti-stop-band anti-soil film The damage of matrix, is proceeded as follows：The surface of the anti-soil film of glass basis is being formed at via adhesive layer setting diaphragm.It is viscous Layer and diaphragm is closed to be removed when the glass basis with anti-soil film is used for product.

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2013-136833 publications

Patent document 2：Japanese Unexamined Patent Publication 2013-244470 publications

The content of the invention

There is following situation in the conventional glass basis with anti-soil film：When removing adhesive layer and diaphragm, anti-soil film A part is peeled off together with adhesive layer from glass basis, the soil resistance such as water repellency and oil repellent of the glass basis with anti-soil film, Wear resistance is reduced.

It is an object of the invention to provide the soil resistance after a kind of removal adhesive layer and diaphragm and excellent in wear resistance The matrix with anti-soil film.

The matrix with anti-soil film of the present invention is that possess anti-soil film, adhesive layer and diaphragm successively in the interarea of transparent base And the matrix with anti-soil film that the adhesive layer and the diaphragm are removed and used, possess the adhesive layer and the protection The blooming of the anti-soil film in the state of film is 10nm~50nm, after removing the adhesive layer and the diaphragm The blooming of the anti-soil film is 3nm~30nm.

In addition, the present invention the matrix with anti-soil film be transparent base interarea possess successively anti-soil film, adhesive layer and Diaphragm and the matrix with anti-soil film that the adhesive layer and the diaphragm are removed and used, remove the adhesive layer and institute The blooming for stating the anti-soil film after diaphragm is 3nm~30nm, { (to possess the adhesive layer and the diaphragm In the state of the anti-soil film blooming)-(remove the anti-soil film after the adhesive layer and the diaphragm Blooming) × 100/ (blooming for possessing the above-mentioned anti-soil film in the state of the adhesive layer and the diaphragm) The rate of change that (%) is represented is 10~60%.

The present invention can provide a kind of soil resistance removed after adhesive layer and diaphragm and the band of excellent in wear resistance is prevented The matrix of dirty film.

Brief description of the drawings

Fig. 1 is the sectional view for the embodiment for representing the matrix with anti-soil film of the present invention.

Fig. 2 is the sectional view for representing to remove the anti-soil film after adhesive layer and diaphragm.

Fig. 3 is the embodiment for schematically showing the manufacture method that can be used in the matrix with anti-soil film of the present invention Device figure.

Embodiment

Hereinafter, the mode for implementing the present invention is illustrated.The present invention is not limited to embodiment disclosed below.Can To be subject to various modifications and displacement to embodiment disclosed below without departing from the scope of the invention.

[matrix with anti-soil film]

Fig. 1 is the sectional view for the embodiment for representing the matrix with anti-soil film of the present invention.The band of embodiment is antifouling The matrix 1 (also referred to as antifouling body) of film possesses transparent base 2 and is formed at the anti-soil film 3 of the interarea of transparent base 2.And then, band The matrix 1 of anti-soil film possesses the adhesive layer 4 on the surface for being removably arranged at anti-soil film 3 and is removably arranged at adhesive layer 4 Surface diaphragm 5.Moreover, the blooming of anti-soil film 3 in the state of possessing adhesive layer 4 and diaphragm 5, in other words, The blooming of anti-soil film 3 before removing adhesive layer 4 and diaphragm 5 is 10nm~50nm.

Matrix 1 with anti-soil film removes adhesive layer 4 and diaphragm 5 and used.Fig. 2 is to represent to remove adhesive layer 4 and protection The sectional view of anti-soil film 3a after film 5.In fig. 2, the optical film of the anti-soil film 3a after adhesive layer 4 and diaphragm 5 is removed Thickness is 3nm~30nm.Compared with the blooming of the anti-soil film 3 before removing adhesive layer 4 and diaphragm 5, the He of adhesive layer 4 is removed The blooming of anti-soil film 3a after diaphragm 5 is small.

It should illustrate, in the matrix 1 with anti-soil film, anti-soil film 3, adhesive layer 4, diaphragm 5 and antireflection film described later As long as being arranged at an at least interarea for transparent base 2, two interareas in transparent base 2 can also be arranged as required to.

Anti-soil film 3 is, for example, that fluorine-containing water-disintegrable silicon compound is carried out as follows hydrolysis-condensation reaction in the interarea of transparent base 2 Formed by film, with soil resistances such as water repellency, oil repellents.In this manual, fluorine-containing water-disintegrable silicon compound refers to have The hydrolyzable silyl group of hydrolyzable group or atom is bonded with the silicon atoms and is further had is bonded to the silicon atom Fluorine-containing organic group compound.In addition, being bonded to silicon atom, constituting the hydrolyzable group or original of hydrolyzable silyl group Son is referred to as hydrolization group.

That is, the hydrolyzable silyl group of fluorine-containing water-disintegrable silicon compound turns into silanol group by hydrolysis, and then, silane Alcohol radical carries out dehydrating condensation between fluorine-containing water-disintegrable silicon compound and generates the siloxanes key shown in-Si-O-Si-, thus Form anti-soil film 3.The major part of fluorine-containing organic group for the silicon atom for constituting siloxanes key is bonded to due to fluorine-containing water-disintegrable silicon The compatibility of compound and transparent base 2 and the near surface for being present in anti-soil film 3.Therefore, the fluorine-containing organic group is passed through Effect, water repellency, oil repellent are gone out in the surface exhibits of anti-soil film 3.In addition, for example using glass basis as transparent base 2 In the case of, the silanol group of the fluorine-containing water-disintegrable silicon compound generated by hydrolysis and the surface for being present in transparent base 2 Hydroxyl carry out dehydration condensation, anti-soil film 3 via siloxanes key formation on transparent base 2.

Moreover, in order to protect anti-soil film 3, diaphragm 5 is set via adhesive layer 4 on the anti-soil film 3 being thusly-formed.Make During with matrix 1 with anti-soil film, adhesive layer 4 and diaphragm 5 are removed.When removing adhesive layer 4 and diaphragm 5, it is impossible to avoid structure Fluorine-containing water-disintegrable silicon compound into the part on the surface of anti-soil film 3 is removed together with adhesive layer 4 from anti-soil film 3.

The blooming of anti-soil film 3 when therefore, to be formed, in other words, remove adhesive layer 4 and diaphragm 5 before it is anti- The blooming of dirty film 3 forms anti-soil film 3 for 10nm~50nm mode.In the anti-soil film 3 with such blooming When surface sets adhesive layer 4 and diaphragm 5 and removes adhesive layer 4 and diaphragm 5, the near surface and not of anti-soil film 3 is constituted The fluorine-containing water-disintegrable silicon compound Nian Jie with transparent base 2 is attached to adhesive layer 4 and is removed.Constitute the fluorinated water of anti-soil film 3 Solution property silicon compound a part be removed, as a result remove the adhesive layer 4 and anti-soil film 3a after diaphragm 5 blooming into For 3nm~30nm.

In the past, when the blooming of the anti-soil film before removing adhesive layer and diaphragm is set as using, in other words, remove The optimum film thickness of anti-soil film after adhesive layer and diaphragm.That is, the optics of the anti-soil film before removal adhesive layer and diaphragm Thickness is optimum film thickness.Then, due to constitute anti-soil film surface fluorine-containing water-disintegrable silicon compound together with adhesive layer by from Transparent base is removed, therefore, and the blooming that the anti-soil film after adhesive layer and diaphragm is removed sometimes is less than optimum film thickness, prevents The soil resistance of dirty film, wear resistance deterioration.On the other hand, constitute present embodiment the matrix 1 with anti-soil film anti-soil film 3 with The blooming of anti-soil film 3a after removal adhesive layer 4 and diaphragm 5 sets for optimal mode.That is, the He of adhesive layer 4 is removed The blooming of anti-soil film 3a after diaphragm 5 is optimum film thickness.So, even if constituting the fluorine-containing water-disintegrable silicon of anti-soil film 3 A part for compound is removed together with adhesive layer 4, due to anti-soil film 3a blooming be it is optimal, therefore, anti-soil film 3a Also good soil resistance, wear resistance are able to maintain that.

Hereinafter, each key element of the matrix 1 with anti-soil film to constituting embodiment is illustrated.

(transparent base)

As long as constitute the matrix 1 with anti-soil film transparent base 2 generally need by anti-soil film 3 assign soil resistance by The transparent base that transparent material is constituted just is not particularly limited, such as preferably by glass, resin or combinations thereof (composite wood Material, stacking material etc.) constitute.In addition, the form for transparent base 2 is also not particularly limited, for example can be with rigidity Tabular, membranaceous etc. with flexibility.

As the resin matrix as transparent base 2, the acrylic resin such as can enumerate polymethyl methacrylate The aromatic polyesters such as the aromatic copolycarbonate system such as matrix, carbonic ester of bisphenol-A resin matrix, polyethylene terephthalate It is resin matrix etc..

In addition, as the polymeric membrane as membranaceous transparent base 2, such as can enumerate PET It is the polyolefin mesenteries such as polyester mesentery, polypropylene, polychloroethylene film, the film of acrylic resin, poly (ether sulfone) film, polyarylate film, poly- Carbonic ester film etc..

In addition, as the glass basis as transparent base 2, as an example, can enumerate using silica and be used as master The simple glass of composition, for example by soda lime glass, alumina silicate glass, pyrex, alkali-free glass, quartz glass Etc. the glass basis of composition.

When using glass as the material of transparent base 2, the composition of glass is preferably plastic, can pass through chemical enhanced place The composition strengthened is managed, sodium is preferably comprised.It is used as such glass, such as preferred alumina silicate glass, sodium-calcium-silicate glass Glass, pyrex, lead glass, alkali barium glass, aluminium pyrex etc..

As the composition of the glass of the material as transparent base 2, it is not particularly limited, can uses with various compositions Glass.As the composition of glass, for example, it can enumerate the composition (being alumina silicate glass) of following glass.

(i) according in terms of the composition that mole % is represented, 50~80% SiO is contained₂, 2~25% Al₂O₃, 0~10% Li₂O, 0~18% Na₂O, 0~10% K₂O, 0~15% MgO, 0~5% CaO and 0~5% ZrO₂Glass

(ii) according in terms of the composition that mole % is represented, 50~74% SiO is contained₂, 1~10% Al₂O₃, 6~14% Na₂O, 3~11% K₂O, 2~15% MgO, 0~6% CaO and 0~5% ZrO₂, and SiO₂And Al₂O₃Content Add up to less than 75%, Na₂O and K₂The content for adding up to 12~25%, MgO and CaO of O content adds up to 7~15% Glass

(iii) according in terms of the composition that mole % is represented, 68~80% SiO is contained₂, 4~10% Al₂O₃, 5~ 15% Na₂O, 0~1% K₂O, 4~15% MgO and 0~1% ZrO₂Glass

(iv) according in terms of the composition that mole % is represented, 67~75% SiO is contained₂, 0~4% Al₂O₃, 7~15% Na₂O, 1~9% K₂O, 6~14% MgO and 0~1.5% ZrO₂, and SiO₂And Al₂O₃Content add up to 71~ 75%, Na₂O and K₂O content adds up to 12~20%, and CaO content is less than 1% glass during containing CaO

In addition, the composition of the glass as the material as transparent base 2, can also enumerate the composition of following glass (being soda lime glass).

(v) according in terms of the composition that mole % is represented, 65~75% SiO is contained₂, 0.1~5% Al₂O₃, 1~15% MgO, 1~15% CaO, Na₂O and K₂O, and Na₂O and K₂The glass for adding up to 10~18% of O content.

(vi) according in terms of the composition that mole % is represented, 65~72% SiO is contained₂, 2~7% Al₂O₃, 5~15% MgO, 3~9% CaO, 13~18% Na₂O, 0~1% K₂O, 0~0.2% TiO₂, 0.01~0.15% Fe₂O₃ With 0.02~0.4% SO₃, and (Na₂O and K₂O content it is total)/(Al₂O₃Content) be 3.5~6.0 glass.

(vii) according in terms of the composition that mole % is represented, 60~72% SiO is contained₂, 1~10% Al₂O₃, 5~ 12% MgO, 0.1~5% CaO, 13~19% Na₂O and 0~5% K₂O, and (RO content)/(RO and R₂O's contains Amount it is total) (in formula, RO represents alkaline earth oxide, R for 0.20~0.42₂O represents alkali metal oxide) glass.

Hereinafter, the content on each composition contained in glass, represents to show with a mole %.

SiO₂It is the composition for the skeleton for constituting glass.In addition, being to reduce splitting when glass surface applies damage (impression) The composition of the generation of line, is the composition for reducing the destructive rate when the glass surface after chemical enhanced applies impression, is also to reduce The composition of thermal coefficient of expansion.SiO₂Content be preferably more than 50%, more preferably more than 60%, more preferably 64% with On, particularly preferably more than 66%.Pass through SiO₂Content be more than 50%, stability as glass can be avoided, acidproof Property, the reduction of weatherability, crumpling resistance.On the other hand, SiO₂Content be preferably less than 80%, more preferably less than 75%, More preferably less than 70%.Pass through SiO₂Content be less than 80%, can avoid because caused by the sticky increase of glass Meltbility reduction.

Al₂O₃It, for making ion-exchange performance and crumpling resistance improve effective composition, is increase surface compression stress to be Composition, is also the composition for being difficult to increase thermal coefficient of expansion more than glass transition point.Al₂O₃Content be preferably 0.1% with On, more preferably more than 2%, more preferably more than 3%, particularly preferably more than 5%.In addition, Al₂O₃Content it is preferred For less than 20%, more preferably less than 15%, more preferably less than 10%.Pass through Al₂O₃Content be more than 0.1%, energy Enough improve ion-exchange performance and crumpling resistance.On the other hand, Al is passed through₂O₃Content be less than 20%, Yin Bo can be avoided The reduction of meltbility caused by the sticky increase of glass.

MgO is to make the composition of stabilization, is also for moderately maintaining the composition needed for thermal coefficient of expansion.MgO's Content is preferably more than 1%, and more preferably more than 2%, more than 3%, more than 4%, more than 5%, more than 8% (particularly preferably More than 8%).In addition, MgO content is preferably less than 15%, more preferably less than 14%, less than 13%, less than 12%, 11% Below, less than 10% (particularly preferably less than 10%).Content by MgO is that the meltability under more than 1%, high temperature becomes good It is good, it is difficult to cause devitrification.On the other hand, it is less than 15% by MgO content, is difficult to cause devitrification to be maintained, can obtain Sufficient ion-exchange speed.

CaO is the composition for improving the meltbility of glass, also for the moderately maintenance effective composition of thermal coefficient of expansion. CaO content is preferably more than 0.05%, more preferably more than 0.1%, more preferably more than 1%, particularly preferably 4% More than.On the other hand, CaO content is preferably less than 10%, more preferably less than 8%, more preferably less than 5%.It is logical The content for crossing CaO is more than 0.05%, can improve meltbility, is less than 10% by CaO content, can deepen surface Compressive stress layers.

Na₂O is the composition that surface compression stressor layers are formed by ion exchange, is also that the meltbility for making glass is improved Composition.Na₂Even if O is that the density of glass is low, thermal coefficient of expansion also becomes big composition, therefore, has for adjustment thermal coefficient of expansion Effect.Na₂O content is preferably more than 10%, and more preferably more than 11%, more preferably more than 12%, particularly preferably More than 13%.On the other hand, Na₂O content is preferably less than 19%, more preferably less than 18%, more preferably 16% Hereinafter, particularly preferably less than 15%.Pass through Na₂O content is more than 10%, can form desired by ion exchange Surface compression stressor layers, pass through Na₂O content is less than 19%, can avoid weatherability and acid proof reduction, can avoid From the generation of the crackle of impression.

K₂O can contain, its content preferably more than 0.1% as needed.K₂, can when O content is more than 0.1% The thermal coefficient of expansion of meltability and appropriateness at a high temperature of maintenance glass.K₂O content is more preferably more than 0.5%, further Preferably more than 1%, particularly preferably more than 2%.In addition, K₂O content is preferably less than 8%.If K₂O content be 8% with Under, then the density of glass diminishes, and the weight of glass diminishes.K₂O content is more preferably less than 6%, more preferably 4% with Under.

Fe₂O₃It is the composition for improving the meltbility of glass.Generally, the Fe in glass₂O₃Visible ray is absorbed, but in thickness of slab In the case of thin glass, because the absorption of light tails off, therefore, it is difficult to turn into problem.In addition, Fe has increase high-temperature heat expansion The effect of coefficient (α max).And then, Fe is due to being the composition for absorbing hot line, therefore, with the thermal convection current for promoting glass melting liquid And improve the homogenieity of glass, the high temperature of bottom brick by preventing melting furnace and extend furnace li` and other effects, using big Type stove and preferably contain in the composition in the smelting process of plate glass that manufactures.Fe₂O₃Content be preferably more than 0.005%, More preferably more than 0.01%, more preferably more than 0.03%, particularly preferably more than 0.06%.On the other hand, if mistake Degree ground contains, then by Fe₂O₃The tone of generation turns into problem, therefore, Fe₂O₃Content be preferably smaller than 0.2%, more preferably less than 0.15%, it is further preferably no larger than 0.12, particularly preferably less than 0.095.

The manufacture method of glass basis is not particularly limited, and can be manufactured by operating as follows：Desired glass is former The continuous input melting furnace of material, preferably carries out heating melting at 1500~1600 DEG C by frit and clarifies, then, by melting Glass supplies to shaped device and is shaped to tabular, carries out slow cooling.

Should illustrate, as the forming method of glass basis, be not particularly limited, can for example use glass tube down-drawing (for example, Overflow downdraw, salivation glass tube down-drawing, again traction method etc.), float glass process, offset the forming methods such as method, pressing.

The thickness of transparent base 2 can suitably be selected according to purposes.The transparent base such as in resin matrix, glass basis In the case that 2 are tabular, the thickness of transparent base 2 is preferably 0.1~5mm, more preferably 0.2~2mm.Particularly using glass Glass matrix carry out chemical intensification treatment described later as transparent base 2 in the case of, for the purpose of lightweight in the case of, in order to Chemical intensification treatment, lightweight are effectively carried out, the thickness of glass basis is preferably below 5mm, more preferably below 3mm. In the case of for the portable electronic device touch panel such as smart mobile phone, tablet personal computer, due to especially paying attention to lightweight, because This, the thickness of glass basis is more preferably below 1mm, particularly preferably below 0.7mm.On the other hand, for automobile In the case of the vehicle-mounted type electronic equipment touch panel such as navigation system, due to more paying attention to rigidity, therefore, glass compared with lightweight The thickness of glass matrix is more preferably more than 0.7mm, particularly preferably more than 1.0mm.

In addition, when the transparent base such as polymeric membrane 2 is membranaceous, the thickness of transparent base 2 is preferably 50~200 μm, more excellent Elect 75~150 μm as.

During using glass basis as transparent base 2, the interarea of glass basis can be implemented to be based on oxygen gas plasma Surface treatment.Alternatively, it is also possible to form silicon oxide film by sputtering etc. in the interarea of glass basis.Handled on these, When carrying out non-glare treated described later, chemical intensification treatment, carried out preferably after non-glare treated, chemical intensification treatment.

(non-glare treated)

In order to assign anti-glare to the matrix 1 with anti-soil film, preferably there is concaveconvex shape in the interarea of transparent base 2.

It is used as the method for forming concaveconvex shape, it is possible to use non-glare treated.As non-glare treated, it is not particularly limited, example Such as when using glass basis as transparent base 2, it is possible to use the interarea of glass basis is implemented at chemically or physically surface The method of reason and concaveconvex shape of the formation with desired surface roughness.

As the method for carrying out chemical non-glare treated, for example, it can enumerate the method for implementing frosted processing (Off ロスト processing). Frosted processing for example can be by the way that the glass basis as handled object be immersed in the mixed solution of hydrogen fluoride and ammonium fluoride To implement.

In addition, as the method for carrying out physics non-glare treated, such as can utilize crystalline silicon dioxide powder, carborundum Powder etc. is blowed with forced air to the so-called blasting treatment of the interarea of glass basis, will be attached with crystalline silicon dioxide powder, carbon The hairbrush water-soaked of SiClx powder etc. and the method for interarea for the glass basis that rubbed with the hairbrush soaked etc..

Wherein, the micro-crack due to being not likely to produce handled object surface is handled as the frosted of chemical surface treatment, be difficult The reduction of mechanical strength is produced, thus, it may be preferable to as the method for implementing surface treatment to glass basis.

In order to repair surface configuration, the interarea that preferred pair so implements the chemically or physically glass basis of non-glare treated enters Row etching process.As etching process, for example, can use etching glass basis being immersed in as the aqueous solution of hydrogen fluoride The method that chemical etching is carried out in solution.Beyond the fluorinated hydrogen of etching solution, the acid such as hydrochloric acid, nitric acid, citric acid can also be contained. By that containing these acid, can suppress because of the cation constituents such as Na ions, the K ions contained by glass basis and hydrogen fluoride The surface of glass basis caused by reaction locally produces precipitate, in addition, can uniformly losing to glass basis Carve.

When being etched, by changing during the dipping of the concentration of etching solution, glass basis in the etch solution Between (hereinafter also referred to " etching period ") etc., etch quantity can be adjusted.Thereby, it is possible to which glass basis is had into bumps The haze value in the face (hereinafter also referred to " non-glare treated face ") of shape is adjusted to desired value.In addition, passing through blasting treatment etc. Physical surface treatment carry out non-glare treated when, although cracked sometimes in transparent base 2, but can by etching process by this The crackle of sample is removed.The depth of crackle in face is most long preferably less than 5 μm, further preferred less than 3 μm.If in the scope, It can then be adequately suppressed because of the rupture strength reduction caused by the internal fissure of face.Crack depth in face can be carried out as follows measure. First, the transparency carrier of multiple (such as 5) same characters is prepared.Then, periodically changed using cerium oxide abrasive grain and ground Mill amount and the interarea of each transparency carrier is ground.Amount of grinding is, for example, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm.Then, if making Micro etching is carried out to the interarea of transparency carrier with the 1mol% HF aqueous solution, then easily confirms the crackle of residual.By using Light microscope (VK-X120 of KEYENCE company systems) confirms that being ground to several μm remains the crackle vestige, can determine and split Line depth.That is, if not remaining crackle vestige when amount of grinding is 5 μm, it may be said that crack depth is less than 5 μm.In addition, passing through erosion Quarter is handled, effect as the dazzle (ギラ Star キ) for the matrix 1 with anti-soil film that can also be inhibited.

In this way, the shape of the interarea as the glass basis after progress non-glare treated and etching process, preferably surface is thick Rugosity (r.m.s. roughness (RMS)) be 0.01~0.5 μm, more preferably 0.01~0.3 μm, more preferably 0.01~ 0.2μm.It is above range by surface roughness (RMS), the haze value of the glass basis after non-glare treated can be adjusted to 3 ~30%.As a result, excellent anti-glare can be assigned to the obtained matrix 1 with anti-soil film.

It should illustrate, surface roughness (RMS) can be according to JIS B 0601：(2001) method is surveyed specified in It is fixed.As surface roughness (RMS) assay method, specifically, laser microscope (VK-9700, KEYENCE company is used System), the aspect of measure to the glass basis after the non-glare treated as sample sets the field range of 200 μm of 300 μ m, determines glass The elevation information of glass matrix.Ended (cutoff) amendment to measured value, obtain the root mean square of obtained height, thus, it is possible to Calculate surface roughness (RMS).As cutoff, 0.08mm is preferably used.

In addition, haze value is the value measured according to method specified in JIS K 7136.

In addition, the surface of the glass basis after carrying out non-glare treated and etching process has concaveconvex shape, if from glass The top observation concaveconvex shape on the surface of matrix, then see the hole of toroidal.So it was observed that toroidal hole size it is (straight Footpath) it is preferably 1 μm~10 μm.By the way that in such scope, anti-dazzle and anti-glare can be had both.

During using glass basis as transparent base 2, in order to improve the intensity of the obtained matrix 1 with anti-soil film, preferably Interarea, non-glare treated face to glass basis implement chemical intensification treatment.

As the method for chemical intensification treatment, it is not particularly limited, it is real by the interarea to glass basis, non-glare treated face Ion-exchange treatment is applied, the superficial layer of compression stress residual is formed in these faces.Specifically, below glass transition point At a temperature of, by the small alkali metal ion of the contained ionic radius in the vicinity in the interarea of glass basis, non-glare treated face (for example, Li Ion, Na ions) the bigger alkali metal ion of ionic radius is replaced into (for example, being Na ions, K ions, phase relative to Li ions It is K ions for Na ions).Thus, in the interarea or non-glare treated face residual compression stress of glass basis, glass basis it is strong Degree is improved.

(antireflection film)

Matrix 1 with anti-soil film can also possess antireflection film between transparent base 2 and anti-soil film 3.In transparent base 2 During with above-mentioned concaveconvex shape, preferably possesses antireflection film on non-glare treated face.

As the composition of antireflection film, as long as the composition of the reflection for that can suppress light is just not particularly limited, for example may be used The refractive index for thinking the high refractive index layer for being more than 1.9 by wavelength 550nm refractive index and wavelength 550nm be less than 1.6 it is low The composition that index layer is laminated.

Antireflection film can comprising each 1 layer of high refractive index layer and low-index layer respectively, can also comprising 2 layers respectively with On high refractive index layer and low-index layer.More than 2 layers respectively of high refractive index layer and low-index layer are included in antireflection film In the case of, it is preferably the form for being alternately laminated high refractive index layer and low-index layer.

Especially for antireflection property is improved, antireflection film is preferably the layered product for being laminated multiple layers, for example should The layer of the layer, more preferably more than 2 layers and less than 4 layers of stacking of preferred more than 2 layers and less than 6 layers of the stacking of layered product.Stacking in this Body is preferably the layered product for being laminated high refractive index layer and low-index layer, preferably by high refractive index layer and low-index layer The respective number of plies it is total obtained from the number of plies in above range.

High refractive index layer, the material of low-index layer are not particularly limited, it may be considered that required antireflection property Degree, productivity ratio etc. are selected.As the material for constituting high refractive index layer, for example, preferably use selected from niobium oxide (Nb₂O₅)、 Titanium oxide (TiO₂), zirconium oxide (ZrO₂), tantalum oxide (Ta₂O₅), more than a kind in silicon nitride (SiN).It is used as the low refraction of composition The material of rate layer, is preferably used selected from silica (SiO₂), the material of the mixed oxide containing Si and Sn, contain Si's and Zr More than a kind in the material of mixed oxide, the material of the mixed oxide containing Si and Al.

From the viewpoint of productivity ratio, refractive index, more preferably above-mentioned high refractive index layer is niobium oxide layer, tantalum oxide layers or nitrogen SiClx layer, above-mentioned low-index layer is silicon oxide layer.

The method of antireflection film film forming is not particularly limited, it is possible to use various film build methods.Particularly preferably pass through arteries and veins The methods such as punching sputtering, AC sputterings, numeral sputtering carry out film forming.By for these methods, forming fine and close film, it can be ensured that durable Property.

For example when carrying out film forming by pulsed sputter, match somebody with somebody in the chamber of non-active gas and the mixed-gas environment of oxygen Transparent base 2 is put, target is selected in the way of as desired composition, by antireflection film film forming.

Now, the gaseous species of the non-active gas in chamber are not particularly limited, it is possible to use argon gas, helium etc. are various Non-active gas.

The pressure in chamber caused by the mixed gas of non-active gas and oxygen is not particularly limited, by for 0.5Pa Hereinafter, the surface roughness that can make antireflection film is easily above-mentioned preferred scope, therefore it is preferred that.If because nonactive The pressure in chamber caused by the mixed gas of gas and oxygen is below 0.5Pa, then is able to ensure that being averaged certainly for flim forming molecule By stroke, flim forming molecule has more multi-energy and reaches transparent base 2.Therefore, it is possible to promote being reconfigured at for flim forming molecule, formed Film closeer and with smooth surface.The lower limit of the pressure in chamber caused by the mixed gas of non-active gas and oxygen does not have It is particularly limited to, such as preferably more than 0.1Pa.

(anti-soil film)

Matrix 1 with anti-soil film possesses anti-soil film 3 in the interarea of transparent base 2.Interarea or anti-dazzle place in transparent base 2 When reason face forms antireflection film, anti-soil film 3 is preferably formed in the surface of the antireflection film.In addition, using implement non-glare treated, When chemical intensification treatment etc. is surface-treated and does not form the glass basis of antireflection film as transparent base 2, the preferred shape of anti-soil film 3 Cheng Yu implements the face of these surface treatments.

As the method for forming anti-soil film 3, as an example, it can enumerate such as inferior method：To have perfluoroalkyl, example The composition of such as silane coupler of the fluoroalkyl fluoroalkyl comprising perfluor (polyoxy alkylidene) chain passes through spin-coating method, dip-coating Method, casting method, slot coated method, spraying process etc. are coated on the method heated after the interarea of transparent base 2；Make to prevent Vacuum vapour deposition that the raw material vapor coating of dirty film 3 is heated after the interarea of transparent base 2 etc..It is close in order to obtain The high anti-soil film 3 of conjunction property, is preferably formed by vacuum vapour deposition.The formation of anti-soil film 3 based on vacuum vapour deposition preferably makes Carried out with the envelope formation containing fluorine-containing water-disintegrable silicon compound with composition.

Envelope formation is the composition containing fluorine-containing water-disintegrable silicon compound with composition, as long as it can be steamed by vacuum Plating method and the composition for forming anti-soil film 3, are not particularly limited.Envelope formation composition can contain fluorine-containing water-disintegrable Any condition beyond silicon compound, only can also be made up of fluorine-containing water-disintegrable silicon compound., can be not as any condition Hinder the scope of effect of the present invention to use, water-disintegrable silicon compound (hereinafter referred to as " the non-fluorine water without fluorine atom can be enumerated Solution property silicon compound "), catalyst etc..

It should illustrate, fluorine-containing water-disintegrable silicon compound and the water-disintegrable silicon compound of arbitrary non-fluorine are matched with envelope and formed When using composition, each compound can be coordinated with the state of script, can also be entered in the form of its partial hydrolysis condensate Row coordinates.Alternatively, it is also possible to be matched with envelope formation use in the form of the mixture of each compound and its partial hydrolysis condensate Composition.

In addition, by fluorine-containing water-disintegrable silicon compound combination of more than two kinds in use, each compound can be with the shape of script State is matched with envelope formation composition, can also be coordinated in the form of respective partial hydrolysis condensate, can also be with 2 The form for planting the partial hydrolysis cocondensation of the compound of the above is coordinated.Alternatively, it is also possible to coordinate these compounds, part The mixture of hydrolytic condensate, partial hydrolysis cocondensation.Wherein, the partial hydrolysis condensate that uses, partial hydrolysis cocondensation Thing is the material of the degree of polymerization for the degree for being capable of vacuum evaporation.It should illustrate, fluorine-containing water-disintegrable silicon compound removes compound in itself In addition, also comprising such partial hydrolysis condensate, partial hydrolysis cocondensation.

(fluorine-containing water-disintegrable silicon compound)

As long as the fluorine-containing water-disintegrable silicon compound anti-soil film 3 used in the formation of anti-soil film 3 has water repellency, oil repellent Compound etc. soil resistance is just not particularly limited.

Specifically, it can enumerate with more than a kind of the base in holo-fluorine polyester, perfluorinated alkylidene and perfluoroalkyl The fluorine-containing water-disintegrable silicon compound of group.These groups are to be bonded to the silicon atom or straight of hydrolyzable silyl group via linking group The form for connecing the fluorine-containing organic group for the silicon atom for being bonded to hydrolyzable silyl group is present.It should illustrate, holo-fluorine polyester is Refer to the group of the divalent for the structure being alternately bonded with etheric oxygen atom with perfluorinated alkylidene.Fluorine-containing water-disintegrable silication is closed The number-average molecular weight (Mn) of thing is preferably 2000~10000, and more preferably 3000~5000.Pass through fluorine-containing water-disintegrable silicon compound Number-average molecular weight (Mn) within the above range, can fully show the soil resistance of anti-soil film 3, wear resistance is also excellent. It should illustrate, the number-average molecular weight (Mn) in this specification refers to the number-average molecular weight measured by gel permeation chromatography.

As described above, obtained from fluorine-containing water-disintegrable silicon compound is reacted in the interarea of transparent base 2 anti-soil film 3 In, above-mentioned fluorine-containing organic group is present in the near surface of anti-soil film 3, and thus anti-soil film 3 has water repellency, oil repellent etc. antifouling Property.As the concrete example of the fluorine-containing water-disintegrable silicon compound with group as described above, following formula (I)s~(V) institute can be enumerated Compound shown etc..

In formula (I), R^f1For the straight-chain of carbon number 1~16 perfluoroalkyl (as alkyl, such as methyl, ethyl, just Propyl group, isopropyl, normal-butyl etc.), R¹For alkyl (such as methyl, ethyl, n-propyl, different of hydrogen atom or carbon number 1~5 Propyl group, normal-butyl etc.), X¹For hydrolyzable group (such as amino, alkoxy, acyloxy, alkenyloxy group, NCO) or Halogen atom (such as fluorine atom, chlorine atom, bromine atoms, iodine atom), m be 1~50, be preferably 1~30 integer, n be 0~ 2nd, preferably 1~2 integer, p is 1~10, is preferably 1~8 integer.

In formula (I), R^f1Carbon number preferably 1~4.In addition, R¹It is preferred that methyl.It is used as X¹Shown hydrolyzable base Group, the preferably alkoxy of carbon number 1~6, more preferably methoxyl group, ethyoxyl.

C_qF_2q+1CH₂CH₂Si(NH₂)₃…(II)

In formula (II), q is more than 1, is preferably 2~20 integer.As the compound shown in formula (II), positive three can be illustrated Fluorine (1,1,2,2- tetrahydrochysenes) propyl group silazane (n-CF₃CH₂CH₂Si(NH₂)₃), positive seven fluorine (1,1,2,2- tetrahydrochysenes) amyl group silicon nitrogen Alkane (n-C₃F₇CH₂CH₂Si(NH₂)₃) etc..

C_rF_2r+1CH₂CH₂Si(OCH₃)₃…(III)

In formula (III), r is more than 1, is preferably 1~20 integer.As the compound shown in formula (III), it can illustrate 2- (perfluoro capryl) ethyl trimethoxy silanes (n-C₈F₁₇CH₂CH₂Si(OCH₃)₃) etc..

In formula (IV), R^f2For-(OC₃F₆)_s- (OC₂F₄)_t- (OCF₂)_u- (s, t, u are each independently 0~200 Integer) shown in divalent straight-chain holo-fluorine polyester, R²、R³Each stand alone as the alkyl (example of the monovalence of carbon number 1~8 Such as methyl, ethyl, n-propyl, isopropyl, normal-butyl).X²、X³It is each independently hydrolyzable group (such as amino, alkane Epoxide, acyloxy, alkenyloxy group, NCO etc.) or halogen atom (such as fluorine atom, chlorine atom, bromine atoms, iodine atom Deng), d, e are each independently 1~2 integer, and c, f are each independently 1~5, preferably 1~2 integer, and a and b are each only On the spot be 2~3 integer.

R^f2In, s+t+u is preferably 20~300, and more preferably 25~100.In addition, R²、R³It is preferred that methyl, ethyl, butyl. It is used as X²、X³The alkoxy of shown hydrolyzable group, preferably carbon number 1~6, more preferably methoxyl group, ethyoxyl.In addition, A and b are respectively preferably 3.

F- (CF₂)_v- (OC₃F₆)_w- (OC₂F₄)_y- (OCF₂)_z(CH₂)_hO(CH₂)_iSi(X⁴)_3-k(R⁴)_k………(V)

In formula (V), v is 1~3 integer, and w, y, z are each independently 0~200 integer, and h is 1~2 integer, and i is 2~20 integer, X⁴For hydrolyzable group, R⁴The alkyl of straight-chain or branched for carbon number 1~22, k is 0~2 Integer.W+y+z is preferably 20~300, and more preferably 25~100.In addition, i is preferably 2~10.X⁴It is preferred that carbon number 1~6 Alkoxy, more preferably methoxyl group, ethyoxyl.R⁴It is preferred that the alkyl of carbon number 1~10.

In addition, there is more than a kind of the base in holo-fluorine polyester, perfluorinated alkylidene and perfluoroalkyl as commercially available The fluorine-containing water-disintegrable silicon compound of group, preferably KP-801 (trade name, chemical industrial company of SHIN-ETSU HANTOTAI system), X-71 (trade name, letter More chemical industrial company's system), KY-130 (trade name, chemical industrial company of SHIN-ETSU HANTOTAI system), KY-178 (trade name, SHIN-ETSU HANTOTAI's chemistry Industrial group's system), KY-185 (trade name, chemical industrial company of SHIN-ETSU HANTOTAI system), (trade name, SHIN-ETSU HANTOTAI chemical industry is public by KY-195 Department system), KY-197 (trade name, chemical industrial company of SHIN-ETSU HANTOTAI system), OPTOOL (registration mark) DSX (trade name, DAIKIN works Industry company system), S-550 (trade name, Asahi Glass system) etc..In above-mentioned commercially available product, more preferably KY-185, KY-195, OPTOOL DSX, S-550.

It should illustrate, when the fluorine-containing water-disintegrable silicon compound of commercially available product is supplied together with solvent, fluorine-containing water-disintegrable silication Compound removes solvent and used.Envelope formation composition is by that above-mentioned fluorine-containing water-disintegrable silicon compound and will be added as needed on Any condition mixed and prepared and for vacuum evaporation.

By making such envelope formation containing fluorine-containing water-disintegrable silicon compound be attached to transparent base 2 with composition Interarea is reacted and forms anti-soil film 3.It should illustrate, can be using public affairs on specific vacuum vapour deposition, reaction condition etc. Method, condition for knowing etc..For example, such anti-soil film 3 can be formed by manufacture method described later.

The blooming preferred 10nm~50nm, more preferably 10~30nm of anti-soil film 3 during formation.During by making to be formed The blooming of anti-soil film 3 is above range, remove the anti-soil film 3a after adhesive layer 4 and diaphragm 5 be able to maintain that it is good Soil resistance and wear resistance.

(adhesive layer)

Matrix 1 with anti-soil film possesses the adhesive layer 4 on the surface for being removably arranged at anti-soil film 3.It is used as adhesive layer 4 Material, preferably when removing adhesive layer 4, the material that adhesive layer 4 can be readily removable from anti-soil film 3.It is used as such adhesive layer 4 Material, adhesive, adhesive of polyurethane series of acrylic acid series etc. can be enumerated.These adhesives are from cementability, fissility Viewpoint consider it is also preferred that.

On the bonding force of adhesive layer 4, the fluorinated water of the composition anti-soil film 3 during from control from the removal adhesive layer 4 of anti-soil film 3 From the viewpoint of the removal amount of solution property silicon compound, 180 degree peel adhesion (foundation of the adhesive layer 4 for acrylic acid series matrix JIS Z 0237) preferred 0.02N/25mm~0.4N/25mm, more preferably 0.05N/25mm~0.2N/25mm.

If the bonding force of adhesive layer 4 is less than 0.02N/25mm, diaphragm 5 can not equably be attached to anti-soil film 3, go During except adhesive layer 4 and diaphragm 5, it is possible to constitute the fluorine-containing water-disintegrable silicon compound on surface of anti-soil film 3 with the quilt of anti-soil film 4 Unevenly remove.In addition, in the conveying of the matrix 1 with anti-soil film, diaphragm 5 is possible to peel off from adhesive layer 4, it is possible to The function of the protection anti-soil film 3 of injury protection film 5.If in addition, the bonding force of adhesive layer 4 is more than 0.4N/25mm, it is likely that viscous The adhesive force for closing 4 pairs of anti-soil film 3 of layer is too strong, when removing adhesive layer 4 and diaphragm 5, constitutes the fluorinated water on the surface of anti-soil film 3 Solution property silicon compound, which is exceeded, necessarily to be removed.Further, since when removing adhesive layer 4 and diaphragm 5, one of adhesive layer 4 Divide the surface for not being removed and remaining in anti-soil film 3, therefore, dirt etc. is produced sometimes bad.And then, in order to remove diaphragm 5 And need larger power, it is possible to it can not equably remove adhesive layer 4 and be peeling inequality.

From the viewpoint of the tack and fissility of anti-soil film 3 and diaphragm 5, the thickness of adhesive layer 4 is preferably 5 μm~ 50μm。

(diaphragm)

Matrix 1 with anti-soil film possesses the diaphragm 5 on the surface for being removably arranged at adhesive layer 4.As diaphragm 5, As long as resinous membranaceous diaphragm is just not particularly limited.In addition, diaphragm 5 can be single layer structure, or It is laminated the sandwich construction of multiple layers such as antistatic layer, hard conating, adhesive layer.

It is the polyester mesentery such as can use polyethylene terephthalate, polyethylene mesentery, poly- as diaphragm 5 The polyolefin mesenteries such as propylene, polychloroethylene film etc..In these films, in terms of with the tack of adhesive layer 4, durability, optics From the aspect of characteristic, preferred polyester mesentery.

The thickness of diaphragm 5 is not particularly limited, such as preferably 5 μm~100 μm, more preferably 10 μm~75 μm.If The thickness of diaphragm 5 is less than 5 μm, then can not fully protect anti-soil film 3 sometimes, if the thickness of diaphragm 5 is more than 100 μm, Occasionally result in cost increase.

[manufacture method of the matrix with anti-soil film]

The manufacture method of the matrix 1 with anti-soil film of the present invention has following process：Film formation process, in transparent base 2 Interarea formation anti-soil film 3；Adhesive layer setting process, adhesive layer 4 is removably arranged at the surface of anti-soil film 3；Diaphragm is set Process is put, diaphragm 5 is removably arranged to the surface of adhesive layer 4.

(film formation process)

Film formation process is that the composition containing fluorine-containing water-disintegrable silicon compound is deposited into the interarea in transparent base 2 and makes it The process reacted and form anti-soil film 3.In film formation process, transparent base 2 interarea with high adhesion formation anti-soil film 3, The thus obtained matrix 1 with anti-soil film can have both the soil resistances such as excellent water repellency, oil repellent and high-caliber wear-resistant Property.

In film formation process, first, the composition containing fluorine-containing water-disintegrable silicon compound is set to be attached to the interarea of transparent base 2 And react it.Above-mentioned antireflection film can also be formed in the interarea of transparent base 2.Have in the interarea of transparent base 2 anti- During reflectance coating, the composition containing fluorine-containing water-disintegrable silicon compound is attached to the surface of antireflection film and react it.In addition, During using the above-mentioned glass basis for implementing the surface treatments such as non-glare treated, chemical intensification treatment as transparent base 2, make containing The composition of fluorine-containing water-disintegrable silicon compound is attached to the surface for implementing surface treatment and reacts it.

As make the composition containing fluorine-containing water-disintegrable silicon compound be attached to transparent base 2 interarea method, as long as It is that the layer institute commonly used approach for forming fluorine-containing water-disintegrable silicon compound using dry process is just not particularly limited, for example, can lifts Go out vacuum vapour deposition, CVD, sputtering method etc..In terms of the decomposition of fluorine-containing water-disintegrable silicon compound when film formation process is suppressed And from the aspect of the simplicity of device, preferred vacuum vapour deposition.

As vacuum vapour deposition, electrical resistance heating, electron beam heating, induction heating method, reaction can be subdivided into Property vapour deposition method, molecular beam epitaxy, hot wall vapour deposition method, ion plating method, cluster ions beam method etc., either method can be applied.From From the aspect of the aspect of decomposition and the simplicity of device of fluorine-containing water-disintegrable silicon compound during suppression film formation process, preferably Electrical resistance heating.Vacuum deposition apparatus is not particularly limited, it is possible to use known device.

Fig. 3 is the embodiment party for schematically showing the manufacture method that can be used in the matrix 1 with anti-soil film of the present invention The figure of the device of formula.Device shown in Fig. 3 is combination of the interarea evaporation containing fluorine-containing water-disintegrable silicon compound in transparent base 2 The device of thing.

Hereinafter, the one side of one side reference picture 3 is illustrated to the manufacture method of the matrix 1 with anti-soil film.Here, to based on electricity The vacuum deposition apparatus of resistance heating is illustrated.During using device shown in Fig. 3, while by delivery section 32 from the left side of figure Film formation process is implemented in conveying one side of transparent base 2 in vacuum chamber 33 to transparent base 2 to the right.

In the vacuum chamber 33 shown in Fig. 3, envelope is formed using the vacuum deposition apparatus 20 based on electrical resistance heating The interarea of transparent base 2 is attached to composition.

From the viewpoint of production stability, the pressure in vacuum chamber 33 is preferably kept at below 1Pa, more preferably Below 0.1Pa.As long as the pressure in vacuum chamber 33 is below 1Pa, it becomes possible to stably carried out based on the true of electrical resistance heating Sky evaporation.

Vacuum deposition apparatus 20 possesses：Container 21 is heated, is arranged at outside vacuum chamber 33, envelope formation is entered with composition Row heating；Pipe arrangement 22, heating container 21 is connected with vacuum chamber 33, and the envelope formation imported from heating container 21 is combined The steam of thing is supplied to manifold 23；And manifold 23, pipe arrangement 22 is connected in vacuum chamber 33, with for will be from pipe arrangement 22 The steam of the envelope formation composition of supply sprays the jet of the interarea to transparent base 2.In addition, in vacuum chamber 33 Interior, transparent base 2 is kept in the jet of manifold 23 mode opposed with the interarea of transparent base 2.

Heating container 21 has and the envelope formation as vapor deposition source can be heated into transpirable temperature with composition Heating part.Envelope formation can suitably be selected with the heating-up temperature of composition according to envelope formation with the species of composition, it is specific and Speech, preferably 30 DEG C~400 DEG C, particularly preferred 50 DEG C~300 DEG C.If the heating-up temperature of envelope formation composition be 30 DEG C with On, then film forming speed becomes good.If the heating-up temperature of envelope formation composition is less than 400 DEG C, it can suppress fluorine-containing The decomposition of water-disintegrable silicon compound, in good anti-soil film 3 of the interarea formation with soil resistance of transparent base 2.

Here, in vacuum evaporation, preferably in the envelope containing fluorine-containing water-disintegrable silicon compound that will be heated in container 21 After formation is warming up to evaporation start temperature with composition, enters to be about to envelope formation and be expelled to a part for the steam of composition The pretreatment of time as defined in system is outer.Envelope formation is macromolecule with fluorine-containing water-disintegrable silicon compound contained in composition Amount, and with molecular weight distribution.Therefore, in the steam for the envelope formation composition for just reaching the stage that start temperature is deposited In, the containing ratio of the low molecular weight compositions easily vaporized can increase, according to circumstances, and low boiling impurity component also increases.By carrying out The pretreatment, can remove the low molecular weight compositions impacted to the durability of anti-soil film 3, low boiling impurity component etc., and then, Can stabilize the composition of the feedstock vapor supplied from vapor deposition source.Thereby, it is possible to be stably formed the anti-soil film that durability is high 3。

Specifically, it can use such as inferior method：Heating container 21 top, relative to matching somebody with somebody that manifold 23 is connected Pipe 22 is provided for the envelope formation at initial stage being expelled to the steam of composition outside heating container 21 in addition is connected to opening and closing The pipe arrangement (not shown) of exhaust outlet freely, the steam is trapped outside heating container 21.

In addition, the temperature of the transparent base 2 during vacuum evaporation is preferably room temperature (20~25 DEG C) to 200 DEG C.If transparent base The temperature of body 2 is less than 200 DEG C, then film forming speed becomes good.More preferably 150 DEG C of the higher limit of the temperature of transparent base 2, it is special Not preferably 100 DEG C.

It should illustrate, in order to prevent the steam condensation of the envelope formation composition supplied from heating container 21, manifold 23 It is preferably provided with heater portion.In addition, in order to prevent from condensing in pipe arrangement 22 from the steam that heating container 21 is supplied, pipe arrangement 22 is preferred Designed in the way of being heated together with heating container 21.

In addition, in order to control film forming speed, variable valve 24 preferably is set in pipe arrangement 22, based on being arranged on vacuum chamber 33 The detected value of interior film thickness gauge 25 controls the aperture of variable valve 24.By setting such composition, supply can be controlled extremely The amount of the steam of the envelope formation composition containing fluorine-containing water-disintegrable silicon compound of the interarea of transparent base 2.Thereby, it is possible to The anti-soil film 3 with desired thickness is formed well in the interarea precision of transparent base 2.It should illustrate, as film thickness gauge 25, Quartz-crystal unit monitor etc. can be used.And then, on the measure of thickness, such as using film analysis X-ray diffraction When counting ATX-G (RIGAKU company systems) as film thickness gauge 25, the interference of reflection X-ray can be obtained by X ray reflection rate method Pattern is simultaneously calculated according to the vibration period of the interference figure.

In this way, the envelope formation containing fluorine-containing water-disintegrable silicon compound is attached to the interarea of transparent base 2 with composition.Enter And, while attachment or after attachment, fluorine-containing water-disintegrable silicon compound is chemically bound in transparent base by hydrolysis-condensation reaction The interarea of body 2, and in intermolecular progress siloxanes bonding, thus as anti-soil film 3.

The hydrolysis-condensation reaction of the fluorine-containing water-disintegrable silicon compound enters while attachment in the interarea of above-mentioned transparent base 2 OK, but in order to fully promote the reaction, the transparent base 2 of anti-soil film 3 will can also be formed with from vacuum chamber as needed After room 33 is taken out, further carry out using heating plate, the heating of constant temperature and humidity cabinet.As the condition of heating, for example Transparent base 2 is heated 10~60 minutes at a temperature of 80~200 DEG C.

It should illustrate, humidification device etc. can also be connected to state of the chamber 33 to humidification in chamber 33 by film formation process It is lower to carry out.Alternatively, it is also possible to be etched after film formation process to the surface of anti-soil film 3 for example, by acid treatment or alkali process Deng the surface roughness (center line average roughness (Ra)) of anti-soil film 3 is adjusted into such as below 10nm.

(adhesive layer setting process, diaphragm setting process)

Then, diaphragm 5 is made to be removably attached to the surface of anti-soil film 3 as above obtained via adhesive layer 4.Will bonding Layer 4 is removably arranged at the method on the surface of anti-soil film 3 and diaphragm 5 is removably arranged to the surface of adhesive layer 4 Method be not particularly limited, can implement in same process, can also implement in different processes, for example, can use The diaphragm 5 for possessing adhesive layer 4 in advance in the face adhered to anti-soil film 3 (hereinafter also referred to " diaphragm with adhesive layer ") is carried It is placed in the method pressurizeed after anti-soil film 3.The setting of the diaphragm with adhesive layer on anti-soil film 3 can continuously be entered OK, now, transparent base 2 is conveyed using laminating machine etc. while the diaphragm with adhesive layer is continuously fed, is placed in Pressurizeed after the interarea of anti-soil film 3, the diaphragm with adhesive layer is attached to anti-soil film 3.Lamination now does not have Be particularly limited to, for example can using be formed with anti-soil film 3 transparent base 2 transporting velocity as 1mm/min~5mm/min, pressurization Power is calculated as 1kgf/cm with line pressure (Line pressures)²~10kgf/m²Carry out.

[removal of adhesive layer and diaphragm]

Matrix 1 with anti-soil film removes above-mentioned set adhesive layer 4 and diaphragm 5 and used.Adhesive layer 4 and diaphragm 5 minimizing technology is not particularly limited, and can remove manually, and stripping off device etc. can also be used to remove.It should illustrate, the application Inventor etc. has found that the value of the blooming of the anti-soil film 3a after peeling off will not increase and decrease because of minimizing technology.

In this way, the blooming of the anti-soil film 3a after removing adhesive layer 4 and diaphragm 5 is 3nm~30nm.Remove bonding When the blooming of anti-soil film 3a after layer 4 and diaphragm 5 is less than 3nm, anti-soil film 3a durability is significantly deteriorated.In addition, When the blooming of anti-soil film 3a after removal is more than 30nm, produce because thickness is uneven, the mist caused by antifouling membrane material cohesion The inequality of degree, is perceived as the quality that optics is uneven, causes infringement design, image to show in appearance.

Additionally, it is preferred that the blooming of the anti-soil film 3a after removing adhesive layer 4 and diaphragm 5 is relative to setting adhesive layer 4 and diaphragm 5 before anti-soil film 3 blooming rate of change be 10%~60%.Thus, adhesive layer 4 and protection are removed Anti-soil film 3a after film 5 possesses excellent soil resistance, and with high abrasion resistance.

Here, anti-soil film 3a is the value obtained by following formula relative to the rate of change of the blooming of anti-soil film 3.

The rate of change of blooming={ (blooming of anti-soil film 3)-(anti-soil film 3a blooming) } × 100/ (blooming of anti-soil film 3) (%) ... (1)

It is excellent with soil resistances such as water repellency, the oil repellents of matrix 1 with anti-soil film of anti-soil film 3 as above obtained, and And with the high abrasion resistance of the wiping of dirt for being resistant to be repeated etc..In addition, the matrix 1 with anti-soil film is due to anti- Possess adhesive layer 4 and diaphragm 5 on dirty film 3, rupture, damage during therefore, it is possible to suppress to transport.Further, since viscous to remove The blooming of anti-soil film 3a after conjunction layer 4 and diaphragm 5 makes removal adhesive layer 4 and diaphragm 5 for the mode of optimum film thickness The blooming of anti-soil film 3 before is above range, and therefore, anti-soil film 3a when using has sufficient blooming, refuses The soil resistances such as aqueous, oil repellent are excellent, and with the high abrasion resistance of the wiping of dirt for being also resistant to be repeated etc..

Embodiment

Hereinafter, the present invention is described in detail by embodiment, but the present invention is not limited to following embodiment. Evaluating in embodiment and comparative example is carried out by following method respectively.

(friction durability (wear resistance))

First, plain weave cotton fine cloth (flat Woven り Cotton cloth gold is installed for the surface of 10mm × 10mm planar metal pressure head in bottom surface Towel) No. 3, the brake pad of friction anti-soil film is made.

Then, using above-mentioned brake pad, determined using the formula of surface wear testing machine 3 (Daiei science essence device makes made) The friction durability of anti-soil film.Specifically, with the bottom surface of above-mentioned brake pad and the surface for the anti-soil film for being formed at transparent base Brake pad is installed on abrasion tester by the mode of contact, to load weight in the way of 1000g to the weight that brake pad applies, With average speed 6400mm/min, one way 40mm in anti-soil film surface reciprocating sliding friction block.Reciprocatingly slide 1 time is Rubbing number 2 times, determine the contact angle of the water on the anti-soil film surface after 50000 end of Rubbing number.The water contact angle on anti-soil film surface Determine using automatic contact angle meter DM-501 (consonance interface science system), the μ L of pure water 1 are added dropwise in anti-soil film to carry out.It is antifouling The measurement site of the water contact angle on film surface is 10 positions, using the arithmetic average of the water contact angle measured at 10 positions as Rub durability.The slip of water contact angle before and after diaphragm of the removal with adhesive layer is fewer, and the reduction of friction durability is got over It is inhibited.

(blooming of anti-soil film)

First, the assay method for possessing the blooming of the anti-soil film of the matrix with anti-soil film of antireflection film is said It is bright.

First, the refractive index that each layer of the antireflection film on transparent base surface is formed to composition is measured.Next, Black tape is pasted at the back side of transparent base, the backside reflection of transparent base is removed.Then, spectral photometry device is utilized (SolidSpec-3700, Shimadzu Seisakusho Ltd.'s system) divides the surface measurements for being formed with the transparent base of antireflection film and anti-soil film Light reflectance spectrum.Then, using the refractive index and the thickness of each layer of each layer for constituting antireflection film measured in advance, it is assumed that antifouling The refractive index of film is 1.35, and the blooming of anti-soil film is calculated by special software.

Then, to not possessing the progress of the assay method of the blooming of the anti-soil film of the matrix with anti-soil film of antireflection film Explanation.

Prepare to be formed with the transparent base of antireflection film respectively and be formed without the transparent base of antireflection film, with identical Condition is in two transparent bases formation anti-soil film.Then, using spectral photometry device similar to the above to be formed with antireflection film and The surface measurements spectral reflection spectrum of the transparent base of anti-soil film.As described above using the folding for each layer for constituting antireflection film Penetrate the thickness of rate and each layer, it is assumed that the refractive index of anti-soil film is 1.35, and the blooming of anti-soil film is calculated by special software. The band for not possessing antireflection film for being set to be formed at the transparent base for being formed without antireflection film under identical conditions by the value is prevented The blooming of anti-soil film in the matrix of dirty film.

The blooming of anti-soil film is number nm~number 10nm, very thin, therefore, standard is difficult to using contact pin type jump instrument True measure, but can be measured by spectral reflection spectrum, ellipsometer.Even if in addition, without using high price as described above Device, the blooming of anti-soil film can also accurately be determined by following method.It is situated between on the surface of transparent base The reflectance spectrum on transparent base surface when forming anti-soil film by antireflection film with the surface of transparent base not via antireflection The reflectance spectrum on film and transparent base surface when directly forming anti-soil film is compared, relative to the reflection that changes of thickness of anti-soil film The change increase of spectrum.Therefore, as described above, by being formed with the transparent base of antireflection film and being formed without antireflection film Transparent base with identical conditions formation anti-soil film method, the blooming of formed anti-soil film can be determined exactly. In embodiment and comparative example, using this method.

(optics is uneven)

First, the matrix configuration with anti-soil film is adjusted into the position of fluorescent lamp so that with antifouling in the top of fluorescent lamp The position of the matrix of film is 1500 Luxs.Then, the light through the matrix with anti-soil film is observed, visually whether produced The inequality of mist degree, color, determines whether inequality.

[embodiment 1]

The matrix with anti-soil film is manufactured by following step.

(1) non-glare treated and etching process

Made using chemically reinforced glass (Dragontrail (registration mark, hereinafter also referred to " DT "), Asahi Glass company system) For transparent base.Then, the non-glare treated for implementing to handle based on frosted to the surface of transparent base by following step.It is first First, acid proof diaphragm is fitted in the side for the not implementing non-glare treated i.e. back side of transparent base.Then, by the transparent base Body impregnates 3 minutes in 3 weight % hydrogen fluoride solutions, removes the dirt on the surface for being attached to transparent base.Then, by transparent base Body impregnates 3 minutes in the mixed solution of 15 weight % hydrogen fluoride and 15 weight % potassium fluorides, to the guarantor that do not fit of transparent base The side of cuticula is that surface carries out frosted processing.

Transparent base after above-mentioned non-glare treated is impregnated into 6 minutes (etching period 6 minutes) in 10% hydrogen fluoride solution, Thus haze value is adjusted to 25%.

(2) chemical intensification treatment

By the transparent base after non-glare treated, dipping lifts after 2 hours in the potassium nitrate for being heated to 450 DEG C and melting, with Thus slow cooling in 1 hour is obtained through chemical enhanced transparent base to room temperature.

(3) film forming of antireflection film (AR films)

For above-mentioned through chemical enhanced transparent base, counnter attack is formed as follows on the side i.e. surface for implementing non-glare treated Penetrate film.

Transparent base is impregnated 4 hours in alkaline solution (Sun Wash TL-75, LION Co. Ltd. system).Then, In vacuum chamber, the mixed gas for the oxygen that 10 volume % are mixed with argon gas is imported while using niobium oxide target (NBO targets, the manufacture of AGC Ceramic Corporations) is in pressure 0.3Pa, frequency 20kHz, power density 3.8W/cm², inversion pulse width 5 Pulsed sputter is carried out under conditions of μ sec, being made up of niobium oxide (niobia) for thickness 13nm is formed on the surface of transparent base The 1st high refractive index layer.

Then, the mixed gas for the oxygen that 40 volume % are mixed with argon gas is imported while using silicon target in pressure Power 0.3Pa, frequency 20kHz, power density 3.8W/cm², pulsed sputter is carried out under conditions of the μ sec of inversion pulse width 5, Thickness 35nm the 1st low-index layer being made up of silica (silica) is formed on 1 high refractive index layer.

Then, the mixed gas for the oxygen that 10 volume % are mixed with argon gas is imported while using niobium oxide target (NBO targets, AGC Ceramic Corporations system) is in pressure 0.3Pa, frequency 20kHz, power density 3.8W/cm², the μ of inversion pulse width 5 Pulsed sputter is carried out under conditions of sec, being made up of niobium oxide (niobia) for thickness 115nm is formed on the 1st low-index layer The 2nd high refractive index layer.

Then, the mixed gas for the oxygen that 40 volume % are mixed with argon gas is imported while using silicon target in pressure Power 0.3Pa, frequency 20kHz, power density 3.8W/cm², pulsed sputter is carried out under conditions of the μ sec of inversion pulse width 5, Thickness 80nm the 2nd low-index layer being made up of silica (silica) is formed on 2 high refractive index layers.

In this way, forming the antireflection film for being laminated with 4 layers of niobium oxide (niobia) layer and the laminated meter of silica (silica).

(4) formation of anti-soil film (AFP films)

First, the fluorine-containing water-disintegrable silicon compound (KY-185, chemical company of SHIN-ETSU HANTOTAI system) as the raw material of anti-soil film is led Enter to heating container.Then, using vavuum pump to being deaerated more than 10 hours in heating container, the solvent carried out in solution is gone Remove, obtain the steam of the envelope formation composition containing fluorine-containing water-disintegrable silicon compound.Then, envelope formation group will be put into The heating container of compound is heated to 270 DEG C.Reach after 270 DEG C, keep the state 10 minutes until temperature stabilization.

Then, the nozzle from connection vacuum chamber and heating container is layered in transparent base to being arranged in vacuum chamber On antireflection film supply envelope is formationed composition steam, progress film forming.

Now, while determining thickness by the quartz-crystal unit monitor being arranged in vacuum chamber while carrying out film forming Until thickness turns into 10nm.Then, the supply of envelope formation composition is stopped at the time of thickness turns into 10nm, from vacuum chamber Take out transparent base in room.The transparent base back side taken out is arranged at heating plate facing downward, carries out 60 at 150 DEG C in an atmosphere Minute heat treatment.

For the anti-soil film being thusly-formed, friction durability and blooming are determined by above-mentioned method.

In addition, being set using laminating machine on the two sides of the transparent base obtained above for being formed with anti-soil film with adhesive layer Diaphragm (EC-9000AS, SUMIRON Co. Ltd. system), manufactures the matrix 1 with anti-soil film.Constitute the diaphragm with adhesive layer Adhesive layer material be acrylic adhesive, 180 degree peel adhesion (foundation of the adhesive layer for acrylic acid series matrix JIS Z 0237) it is 0.06N/25mm, diaphragm is polyethylene terephthalate (hereinafter also referred to " PET ") mesentery, is protected The thickness of cuticula is 25 μm.

Then, the diaphragm with adhesive layer on anti-soil film surface is removed, by above-mentioned method to removing with adhesive layer It is uneven that anti-soil film after diaphragm determines friction durability, blooming and optics.

[embodiment 2]

Without non-glare treated, antireflection film is not formed, in addition, the shape on transparent base similarly to Example 1 Into blooming 15nm anti-soil film.In addition, being set similarly to Example 1 on the two sides for being formed with the transparent base of anti-soil film Diaphragm (EC-9000AS, SUMIRON Co. Ltd. system) with adhesive layer, manufactures the matrix 2 with anti-soil film.With embodiment 1 Friction durability, blooming and the optics for similarly determining anti-soil film are uneven.

[embodiment 3]

Without non-glare treated, antireflection film is not formed, in addition, the shape on transparent base similarly to Example 1 Into blooming 25nm anti-soil film.In addition, being formed with the transparent base of anti-soil film using laminating machine similarly to Example 1 Two sides set the diaphragm (UA-3000AS, SUMIRON Co. Ltd. system) with adhesive layer, manufacture the matrix 3 with anti-soil film. The material for constituting the adhesive layer of the diaphragm with adhesive layer is polyurethane series adhesive, and adhesive layer is for acrylic acid series matrix 180 degree peel adhesion (according to JIS Z 0237) is 0.15N/25mm, and diaphragm is PET mesenterys, and the thickness of diaphragm is 25 μ m.Friction durability, blooming and the optics for determining anti-soil film similarly to Example 1 are uneven.

[embodiment 4]

Without non-glare treated, antireflection film is not formed, in addition, the shape on transparent base similarly to Example 1 Into blooming 40nm anti-soil film.In addition, being formed with the transparent base of anti-soil film using laminating machine similarly to Example 1 Two sides the diaphragm (RP-207, day east electrician company system) with adhesive layer is set, manufacture the matrix 4 with anti-soil film.Constitute band The material of the adhesive layer of the diaphragm of adhesive layer is acrylic adhesive, and adhesive layer is shelled for the 180 degree of acrylic acid series matrix It is 0.1N/25mm from bonding force (according to JIS Z 0237), diaphragm is PET mesenterys, and the thickness of diaphragm is 25 μm.With implementation Friction durability, blooming and the optics that example 1 similarly determines anti-soil film are uneven.

[embodiment 5]

Without non-glare treated, in addition, form blooming 10nm's on transparent base similarly to Example 1 Anti-soil film.In addition, setting band bonding on the two sides for being formed with the transparent base of anti-soil film using laminating machine similarly to Example 1 The diaphragm (Y16FS, Sun Aization grind company system) of layer, manufactures the matrix 5 with anti-soil film.Constitute the diaphragm with adhesive layer The material of adhesive layer is acrylic adhesive, 180 degree peel adhesion (foundation JIS of the adhesive layer for acrylic acid series matrix Z 0237) it is 0.3N/25mm, diaphragm is PET mesenterys, and the thickness of diaphragm is 25 μm.Determine similarly to Example 1 antifouling Friction durability, blooming and the optics of film are uneven.

[embodiment 6]

Using fluorine-containing water-disintegrable silicon compound (OPTOOL DSX, chemical company of SHIN-ETSU HANTOTAI system) as the raw material of anti-soil film, no Non-glare treated is carried out, antireflection film is not formed, in addition, forms blooming on transparent base similarly to Example 1 30nm anti-soil film.In addition, being set using laminating machine similarly to Example 1 on the two sides for being formed with the transparent base of anti-soil film Diaphragm (RP-207, day east electrician company system) with adhesive layer, manufactures the matrix 6 with anti-soil film.Similarly to Example 1 Friction durability, blooming and the optics for determining anti-soil film are uneven.

[embodiment 7]

Antireflection film is not formed, in addition, forms blooming 20nm's on transparent base similarly to Example 1 Anti-soil film.In addition, setting the diaphragm with adhesive layer on the two sides for being formed with the transparent base of anti-soil film similarly to Example 1 (EC-9000AS, SUMIRON Co. Ltd. system), manufactures the matrix 7 with anti-soil film.Anti-soil film is determined similarly to Example 1 Friction durability, blooming and optics it is uneven.

[comparative example 1]

Without non-glare treated, antireflection film is not formed, in addition, the shape on transparent base similarly to Example 1 Into blooming 10nm anti-soil film.In addition, being formed with the transparent base of anti-soil film using laminating machine similarly to Example 1 Two sides set the diaphragm (TG-3030, SUMIRON Co. Ltd. system) with adhesive layer, manufacture the matrix 1C with anti-soil film. The material for constituting the adhesive layer of the diaphragm with adhesive layer is acrylic adhesive, and adhesive layer is for acrylic acid series matrix 180 degree peel adhesion (according to JIS Z 0237) is 3.0N/25mm, and diaphragm is PET mesenterys, and the thickness of diaphragm is 25 μ m.Friction durability, blooming and the optics for determining anti-soil film similarly to Example 1 are uneven.

[comparative example 2]

Without non-glare treated, antireflection film is not formed, in addition, the shape on transparent base similarly to Example 1 Into blooming 60nm anti-soil film.In addition, being set similarly to Example 1 on the two sides for being formed with the transparent base of anti-soil film Diaphragm (EC-9000AS, SUMIRON Co. Ltd. system) with adhesive layer, manufactures the matrix 2C with anti-soil film.With embodiment 1 Friction durability, blooming and the optics for similarly determining anti-soil film are uneven.

By what is manufactured in the matrix 1~7 with anti-soil film and comparative example 1~2 that are manufactured in embodiment 1~7 with anti-soil film The uneven measurement result of matrix 1C~2C manufacturing condition, the friction durability of anti-soil film, blooming and optics is shown in table 1. In addition, the rate of change of the blooming of the anti-soil film calculated by above-mentioned formula (1) is shown in into table 1.

[table 1]

As shown in table 1, it is known that make to possess the blooming of anti-soil film in the state of adhesive layer and diaphragm for 10nm~ The matrix 1 with anti-soil film that 50nm and the blooming for making the anti-soil film after removal adhesive layer and diaphragm are 3nm~30nm ~7 can suppress the reduction of the wear resistance because of the anti-soil film caused by removal adhesive layer and diaphragm.And then, it is known that band anti-soil film Matrix 1~7 it is uneven without optics, possess the excellent transparency.

Symbol description

1 ... the matrix with anti-soil film, 2 ... transparent bases, 3,3a ... anti-soil films, 4 ... adhesive layers, 5 ... diaphragms.

Claims

1. a kind of matrix with anti-soil film, it is characterised in that be transparent base interarea possess successively anti-soil film, adhesive layer and Diaphragm and the matrix with anti-soil film that the adhesive layer and the diaphragm are removed and used,

The blooming for possessing the anti-soil film in the state of the adhesive layer and the diaphragm is 10nm~50nm,

The blooming for removing the anti-soil film after the adhesive layer and the diaphragm is 3nm~30nm.

2. a kind of matrix with anti-soil film, it is characterised in that be transparent base interarea possess successively anti-soil film, adhesive layer and Diaphragm and the matrix with anti-soil film that the adhesive layer and the diaphragm are removed and used,

The blooming for removing the anti-soil film after the adhesive layer and the diaphragm is 3nm~30nm,

With (blooming for possessing the anti-soil film in the state of the adhesive layer and the diaphragm)-(remove described The blooming of the anti-soil film after adhesive layer and the diaphragm) } × 100/ (possess the adhesive layer and the protection The blooming of the anti-soil film in the state of film) (%) represent rate of change be 10~60%.

3. the matrix with anti-soil film as claimed in claim 1 or 2, wherein, the adhesive layer for acrylic acid series matrix 180 It is 0.02N/25mm~0.4N/25mm to spend peel adhesion (according to JIS Z 0237).

4. such as matrix according to any one of claims 1 to 3 with anti-soil film, wherein, the transparent base is glass basis.

5. such as matrix according to any one of claims 1 to 4 with anti-soil film, wherein, prevent in the transparent base with described Antireflection film is further equipped between dirty film.

6. such as matrix according to any one of claims 1 to 5 with anti-soil film, wherein, the interarea of the transparent base has Concaveconvex shape.

7. such as matrix according to any one of claims 1 to 6 with anti-soil film, wherein, the anti-soil film is by containing fluorinated water The envelope formation of solution property silicon compound is formed with composition.