CN102858707A - Method for producing glass member, and planar lens and glass paste - Google Patents

Abstract

Disclosed is a method for producing a glass member using a paste that contains glass powder wherein the paste has a long life and the adherence of the substrate and paste is superior. Also disclosed are an all-glass planar lens suitable for Fresnel lenses and the like and a glass paste optimal for producing this planar lens. Specifically, the paste has a boron oxide content of 40 mol% or less in a glass powder and a binder having hydroxyl groups, and the composition on a glass substrate differs from the substrate. In addition a glass optically functional part contains 40-64% SiO2, 5-35% B2O3, 2-30% ZnO, 1 -10% Al2O3, 10-22% of one or more of Li2O, Na2O and K2O, and 0-10% BaO+SrO.

Description

The manufacture method of glass member made, planar lens and glass paste

Technical field

The present invention relates to be suitable for to make the manufacture method that Fresnel lens, microlens array, biconvex lens etc. have the glass optics processed of small concavo-convex optics, and the planar lens of the used glass systems such as Fresnel lens such as the stroboscopic lamp of the beam condensing unit of solar cell or digital camera, and be suitable for making the glass paste of this planar lens most.

Background technology

The manufacture method (patent documentation 1) of the known glass member made that has document to disclose to form trickle concaveconvex shape on the surface.

This patent documentation 1 discloses slurry is coated with/is dried to stratiform, will press on pulp layer with the concavo-convex corresponding shaping dies that forms and the shape of shaping dies is molded into the method for pulp layer on the surface of glass substrate.

In addition, patent documentation 1 also discloses to use and has had with the roller mould of the concavo-convex corresponding recess that forms, in the recess filling paste of this mould and lip-deep method dry, slurry is transferred to glass substrate from the recess of roller mould.

In addition, patent documentation 1 material that is suitable for the glass powder of above-mentioned manufacture method in its 0018th section conduct discloses and has comprised lead silicate glass and the so low glass of temperature of fusion of zinc, lead or phosphate glass.

According to the inventor's research, slurry must realize and glass substrate between adaptation and the storage stability (slurry life-span) of long term maintenance slurry form.For this reason, require slurry to possess the low characteristic of adaptation between adaptation between glass substrate and the tackiness agent excellent and glass powder and the tackiness agent.

In addition, in general, the used planar lenss such as Fresnel lens of the stroboscopic lamp of solar cell or digital camera are normally resinous.

Patent documentation 2 discloses the planar lens of glass system.

This patent documentation 2 discloses the method for making microlens array with the method for burning till behind the formation glass paste film, as the composition of the glass paste that uses in the method, discloses 2 kinds of glass powders.The composition of the 1st kind of glass powder is: bismuth oxide 42.9 % by weight, boron oxide 18.2 % by weight, barium oxide 16.9 % by weight, zinc oxide 13.0 % by weight, silicon oxide 9.1 % by weight (the 0121st section).The composition of the 2nd kind of glass powder is: silicon oxide 46.8 % by weight, boron oxide 23.4 % by weight, Lithium Oxide 98min 16.9 % by weight, barium oxide 4.0 % by weight (the 0130th section).

Patent documentation

Patent documentation 1: Japanese patent laid-open 10-101373 communique

Patent documentation 2: Japanese patent laid-open 9-230112 communique

Summary of the invention

Invent technical problem to be solved

But, 1 pair of patent documentation be suitable for above-mentioned manufacture method glass powder material with no specific disclosure of or the hint.

On the other hand, patent documentation 2 disclosed the 1st kind of glass powders contain bismuth oxide.The 2nd kind of glass powder of patent documentation 2 then contains a large amount of Lithium Oxide 98mins.It % by mole is more than 30 % by mole that the content of this Lithium Oxide 98min is scaled.Here, bismuth oxide and Lithium Oxide 98min all be when the method for glass powder is burnt till in use in firing process the composition of rising glass flow, the problem of the shape before existence can not keep burning till.Therefore, the glass powder of patent documentation 1 record is unsuitable for the glasswork that Fresnel lens needs acute angle shape like this.

The present invention is in view of the practical situation of above-mentioned prior art propose, and the manufacture method of using the glass component that is suitable for making the glass powder with small concavo-convex optics is provided.

Even the present invention also provides and has all made with glass and lens that Fresnel lens has complicated shape like this also can correctly form the planar lens of desired shape, and is suitable for making the glass paste of this planar lens most.

The technique means of technical solution problem

In order to achieve the above object, the manufacture method of glass member made of the present invention provides the manufacture method of following glass member made, namely, it is the manufacture method of concavo-convex glass member made that has formed the regulation shape of glass system on the surface of glass substrate, possesses following operation: use the slurry comprise glass powder, tackiness agent and solvent, form the concavo-convex operation that forms of the described regulation shape that consisted of by described glass powder and tackiness agent on the surface of described glass substrate; Concavo-convexly remove tackiness agent, then make the heating process of glass powder welding with surface from described glass substrate forms, and the described glass powder of described slurry contains boron oxide and its content below 40 % by mole, and described tackiness agent has hydroxyl.

In the manufacture method of glass member made so of the present invention, described formation operation preferably possesses following operation: described slurry is coated the surface of glass substrate and the operation that forms pulp layer, remove described solvent from this pulp layer, press on the pulp layer of having removed described solvent with the shaping dies that will have with the concavo-convex corresponding shape that forms, formation has the concavo-convex pulp layer of regulation shape, the operation of then this shaping dies being taken off from pulp layer.In this process, before pressing described shaping dies, the pulp layer that preferably will remove described solvent is heated to the softening temperature of described tackiness agent.

In the manufacture method of glass member made so of the present invention, described formation operation also can possess to be coated described slurry concavo-convex roller mould with regulation shape, is formed the operation of the concavo-convex pulp layer with regulation shape by this roller mould at described glass baseplate surface.

Described tackiness agent is butyral resin preferably.

The content of the boron oxide that described glass powder is contained is preferably more than 3 % by mole, below 40 % by mole.

In addition, planar lens of the present invention provides following planar lens, namely, form by forming the optical function section that different glass consists of from described glass substrate at glass substrate, the glass that consists of this optical function section is the glass that comprises following composition with % by mole expression of oxide compound benchmark: silicon oxide (SiO ₂) 40～64%, boron oxide (B ₂O ₃) 5～35%, zinc oxide (ZnO) 2～30%, aluminum oxide (Al ₂O ₃) 1～10%, Lithium Oxide 98min (Li ₂O), sodium oxide (Na ₂O) and potassium oxide (K ₂O) at least a adds up to 10～22%, and at least a of barium oxide (BaO) and strontium oxide (SrO) is 0～10%.

In planar lens so of the present invention, except as the occasion that contains from the impurity of other compositions, the glass that consists of described optical function section is in fact not bismuth-containing compound, lead compound and phosphorus compound preferably.In addition, described glass substrate is preferably 75 * 10 at 50～350 ℃ average coefficient of linear expansion ^-7～100 * 10 ^-7/ ℃.Moreover the second-order transition temperature of described glass substrate is preferably 550～670 ℃.

In addition, glass paste of the present invention provides following glass paste,, comprises glass powder, tackiness agent and solvent that is, and wherein glass powder comprises following composition with % by mole expression of oxide compound benchmark: silicon oxide (SiO ₂) 40～64%, boron oxide (B ₂O ₃) 5～35%, zinc oxide (ZnO) 2～30%, aluminum oxide (Al ₂O ₃) 1～10%, Lithium Oxide 98min (Li ₂O), sodium oxide (Na ₂O) and potassium oxide (K ₂O) at least a adds up to 10～22%, and at least a of barium oxide (BaO) and strontium oxide (SrO) is 0～10%.

In glass paste so of the present invention, except as the occasion that contains from the impurity of other compositions, described glass is in fact not bismuth-containing compound, lead compound and phosphorus compound preferably.In addition, described tackiness agent preferably has the resin of hydroxyl, and described tackiness agent is more preferably butyral resin.

"～" that represents above-mentioned numerical range uses as the implication of lower value and upper restriction with the numerical value of record before and after it, below "～" in this specification sheets all use with same implication.

The invention effect

According to the manufacture method of the glass member made of the present invention with above-mentioned formation, can provide to be suitable for most making to have method small concavo-convex optics, make the glass member made with the slurry that comprises glass powder and tackiness agent.

In addition, according to planar lens of the present invention and glass paste with above-mentioned formation, the planar lens that can have the glass systems such as Fresnel lens of desired shape with easy method acquisition.

Description of drawings

Fig. 1: the synoptic diagram of an example that (A)～(E) is the manufacture method of explanation glass member made of the present invention.

Fig. 2: the schema of an example that the manufacture method of glass member made of the present invention is described.

Fig. 3: the synoptic diagram of an example of the Fresnel lens made from the manufacture method of glass member made of the present invention is the view of observing from optical axis direction (A), (B) is the A-A line sectional view of (A).

Fig. 4: another the routine synoptic diagram that (A)～(D) is the manufacture method of explanation glass member made of the present invention.

Fig. 5: with the synoptic diagram of planar lens of the present invention for an example of Fresnel lens, being the view of observing from optical axis direction (A), (B) is the A-A line sectional view of (A).

Embodiment

Describe with reference to the accompanying drawings manufacture method, planar lens and the glass paste of glass member made of the present invention in detail.

Fig. 1 schematically shows the accompanying drawing that in the example of manufacture method of glass member made of the present invention glass baseplate surface is formed concavo-convex method.Fig. 2 is the accompanying drawing of flow process of an example of the manufacture method of expression glass member made of the present invention.

Example shown in Figure 1 is to utilize manufacture method of the present invention to make the example of the sort of round Fresnel lens that property illustrated in Figure 3 represents.Fig. 3 (A) is the view of observing from the optical axis direction of lens, and Fig. 3 (B) is the sectional view at the A-A line place of Fig. 3 (A).

As shown in Figure 3, this Fresnel lens 10 is made of glass substrate 12 and the lens section 14 that is formed at these glass substrate 12 surfaces, and this lens section 14 has the concavo-convex of the regulation shape that consists of Fresnel lens.Glass substrate 12 and lens section 14 all are glass system, and the not directly welding by binder layer etc. (not using tackiness agent), contact are bonding.

Lens section 14 is formed by the slurry that comprises glass powder (being frit) (following this is called glass paste, or simply be called slurry).

Glass substrate 12 is sheet glass commonly used.

The formation material of used glass substrate 12 is not particularly limited in the manufacture method of the present invention, can extensively utilize various glass materials.As an example, can exemplify soda lime glass, alumina silicate glass, borate glass, lithium alumina silicate glass, silica glass, pyrex, non-alkali glass etc.

Manufacture method of the present invention is suitable for making the such optics of Fresnel lens 10 of accompanying drawing example.Therefore, glass substrate 12 forms with the glass that the transparency is high, optical characteristics is excellent.

Manufacture method of the present invention is used the slurry that comprises glass powder on the surface of this glass substrate 12, forms to have the concavo-convex lens section 14 that becomes the regulation of Fresnel lens shape.

Slurry to major general's glass powder and tackiness agent dispersed/dissolved forms in solvent.Perhaps, slurry is to be mixed by glass powder and carrier (so-called carrier is the mixture of tackiness agent and solvent) at least.Here, among the present invention, as the glass powder of sneaking into slurry, use and contain the content of boron oxide and this boron oxide at the glass powder below 40 % by mole.In addition, as the tackiness agent of sneaking into slurry, use the tackiness agent with hydroxyl (OH yl).

By having this formation, the present invention has realized reaching simultaneously adaptation between glass substrate 12 and the slurry and the manufacturing of the enough glass member made slurry life-span, stable, high-quality.

As hereinafter describing in detail, in the manufacture method of accompanying drawing example, slurry forms pulp layer 20 in glass substrate 12 coatings, dry (being desolventizing).Afterwards, press pulp layer 20 with shaping dies 24, then shaping dies 24 is taken off from pulp layer 20, pulp layer 20 mold pressings are gone out the shape of lens section 14.

Subsequently, carry out the unsticking mixture and process and burn till processing, formed the lens section 14 of Fresnel lens effect on glass substrate 12 surfaces by the pulp layer 20 after the mold pressing, make Fresnel lens 10.

In order to press suitably pulp layer 20, need strong pressing force to a certain degree.Therefore, if a little less than the adaptation between pulp layer 20 and the glass substrate 12, then after pressing with shaping dies 24, pulp layer 20 can be raised with shaping dies 24 when taking off shaping dies 24, and the result peels off from glass substrate 12.Pulp layer 20 is just peeled off and can not be manufactured a product suitably from glass substrate 12.

On the other hand, slurry is prepared by dropping into to stir behind the compositions such as glass powder and tackiness agent in solvent.Perhaps, prepare by stirring behind the compositions such as input glass powder in carrier.Here, slurry is not directly to use afterwards in preparation, normally re-uses through behind the certain hour.In addition, consider from productivity and operation efficiency, common way be preparation with the slurry of repeatedly making corresponding amount after it is taken good care of, then the share when at every turn making is taken.

Therefore, slurry being required its state that can be used as the slurry use after adjustment is that storage stability (slurry life-span) is long.

The inventor is studied this, found that, for guaranteeing glass substrate 12 and slurry (being the pulp layer after the pulp layer 20(desolventizing in the accompanying drawing example)) between good adaptation, must use butyral resin etc. to contain the tackiness agent of hydroxyl.

On the other hand, common glass powder contains boron oxide.

But when preparing slurry with the glass powder that contains a large amount of boron oxides with the tackiness agent that contains hydroxyl, slurry can become glue rather than pulp-like in the short period of time, and the situation that can't obtain enough slurry life-spans is multiple.

The inventor has further carried out repeatedly research for solving such problem.

Found that, because in the contained boron oxide of glass powder and the tackiness agent specific reaction occurs and powerful combination between the contained hydroxyl, so interior slurry of short period of time becomes glue.Also find, the result of this reaction be originally should bring into play and glass substrate 12 between the hydroxyl of tackiness agent of adhesive effect lacked, the adaptation between glass substrate 12 and the slurry has also descended.

In addition, if the adaptation between tackiness agent and the glass powder is high, unsticking mixture variation then can't be processed with the unsticking mixture and fully remove tackiness agent, also might after carbonization and to the optical characteristics such as transparency generation detrimentally affect when burning till.

The inventor has carried out repeatedly research again, found that, the content by making boron oxide in the glass powder has been guaranteed the adaptation between glass substrate 12 and the slurry, and can have been obtained the sufficiently long slurry life-span below 40 % by mole.

That is to say, the present invention is when making glass baseplate surface and have the concavo-convex glass component of the regulation shape that formed by glass powder, comprise tackiness agent with hydroxyl and boron oxide content at the slurry of the glass powder below 40 % by mole by use, satisfied adaptation between the glass powder of the excellent and same glass of adaptation between glass substrate 12 and the tackiness agent and the tackiness agent low preferably be considered to opposite characteristic, realized simultaneously and glass substrate between adaptation and slurry life-span.

Among the present invention, the glass powder of sneaking into slurry contains the content of boron oxide and boron oxide below 40 % by mole.

If the boron oxide content in the glass powder surpasses 40 % by mole, then can not obtain as previously mentioned enough slurry life-spans, can not fully obtain the adaptation between glass substrate 12 and the slurry.

In addition, the content lower limit of boron oxide in the glass powder is not particularly limited.But the content of boron oxide is many, and then " Ts-Tg " described later value has the tendency that becomes large, thus the boron oxide content in the glass powder more than 3 % by mole, especially more than 5 % by mole for well.

In addition, among the present invention, the softening temperature (Ts) of sneaking into the glass powder of slurry and second-order transition temperature (Tg) poor, namely " Ts-Tg " be the bigger the better.

As described later, in the manufacture method of the present invention, form the regulation shape that consisted of by aforementioned slurry concavo-convex on the surface of substrate 12 after, carry out burning till of unsticking mixture and glass powder.

Here, the glass powder that " Ts-Tg " is large (glass material) is considered to the little material of viscosity slope of a curve, i.e. viscosity variation varies with temperature little material.That is to say, research according to the inventor, " Ts-Tg " according to glass powder, can present weakness (ダ レ) (concaveconvex shape of formation is not obvious) when burning till, " Ts-Tg " is larger, weakness when then burning till is fewer, burn till before and burn till after change of shape fewer (being that shape-holding property is better).

Therefore, " Ts-Tg " large glass powder, the weakness when burning till is fewer, can make the glass member made with high precision.

Consider above problem points, " Ts-Tg " of used glass powder more than 110 ℃, especially more than 120 ℃ for well.

In the manufacture method of the present invention, used glass powder being not particularly limited, (is boron oxide (B as long as satisfy aforementioned prerequisite ₂O ₃) content below 40 % by mole, more preferably 5～35 % by mole), the glass powder that can extensively utilize various glass materials to form.

For example, as this glass powder, preferably exemplify and be selected from SiO ₂-B ₂O ₃-Al ₂O ₃System, SiO ₂-B ₂O ₃-Bi ₂O ₃System, B ₂O ₃-ZnO-Bi ₂O ₃System, SiO ₂-B ₂O ₃-ZnO system, SiO ₂-BaO-B ₂O ₃System, Bi ₂O ₃-BaO-ZnO system, B ₂O ₃-ZnO-La ₂O ₃System, P ₂O ₅-B ₂O ₃-R ' ₂O-R " O-TiO ₂-Nb ₂O ₅-WO ₃-Bi ₂O ₃System, B ₂O ₃-Bi ₂O ₃System, B ₂O ₃-ZnO system, ZnO-B ₂O ₃-SiO ₂-Al ₂O ₃System, Bi ₂O ₃-B ₂O ₃-SiO ₂-Al ₂O ₃System, Bi ₂O ₃-ZnO-B ₂O ₃-SiO ₂System, Bi ₂O ₃-ZnO-B ₂O ₃-SiO ₂-Al ₂O ₃System and SiO ₂-B ₂O ₃-Nb ₂O ₃-R ' ₂At least a glass of O system.In addition, in the above-mentioned formula, R ' represents alkali metal, R " expression alkaline-earth metal element.

Glass powder can multiple and usefulness.Multiple glass powder and time spent, the contained boron oxide content of each glass powder respectively below 40 % by mole for well.

In addition, in the glass powder, except above-mentioned main component, also can add the titanium oxide (TiO as added ingredients ₂), zirconium white (ZrO ₂), stannic oxide (SnO ₂), Indium sesquioxide (In ₂O ₃), vanadium oxide (V ₂O ₅), cerium oxide (CeO ₂) and the various materials such as fluorine.

Glass powder is for good by the glass powder that forms than the low glass more than 50 ℃ of the softening temperature of glass substrate 12.

If the softening temperature of glass powder is lower more than 50 ℃ than the softening temperature of glass substrate 12, then glass powder can carry out under than the low temperature of the softening temperature of glass substrate the welding of glass substrate, therefore in firing process described later, glass substrate 12 thermal distortions can be suitably prevented, the welding of glass powder of concavo-convex (being lens section 14 in the accompanying drawing example) of regulation shape can be formed.For example, when glass substrate 12 is soda-lime glass, softening temperature near 730 ℃, so the softening temperature of glass powder below 680 ℃ for well.

On the other hand, the softening temperature of glass powder is for good than the high high temperature of the decomposition temperature of tackiness agent contained in the slurry.The softening temperature of glass powder is according to the kind of tackiness agent and difference, but especially more than 350 ℃ for well.

Have the glass powder of this softening temperature by use, in unsticking mixture operation described later, can prevent suitably that the welding between unsticking mixture and the glass powder from occuring simultaneously.

Moreover for the stress that prevents from more effectively being caused by thermal expansion and by peeling off of causing of this stress etc., the thermal expansivity of glass powder and glass substrate 12 is to be close to.

For example, use soda-lime glass (thermal expansivity 80～90 * 10 ^-7/ ℃) during as glass substrate 12, the thermal expansivity of glass powder preferably 50～100 * 10 ^-7/ ℃.

The median size of glass powder below 10 μ m for well.

Median size by making glass powder is below 10 μ m, can prevent that the surfaceness of filming that glass powder slurry coating/drying forms from becoming large, the transfer printing of mold shape can be in pressurization operation described later (mold pressing), formed more effectively, the breakage of shaping dies can also be prevented more effectively.

The lower limit of particle diameter is not particularly limited, but the cost consideration that glass is pulverized when making glass powder, with above for well about 0.5 μ m.

As previously mentioned, slurry mixes to major general's glass powder and tackiness agent input solvent.Perhaps, slurry is mixed by glass powder and carrier at least.In addition, among the present invention, tackiness agent is the tackiness agent that contains hydroxyl.

As previously mentioned, tackiness agent has and remains on slurry on the glass substrate 12 and make pulp layer 20 present not the effect of the adaptation of and glass that peel off from glass substrate 12 in pressurization operation described later.In addition, the tackiness agent hardness of filming that also coating of performance adjustment slurry forms in the pressurization operation, the effect that improves the shape transferred thereon of shaping dies.

Tackiness agent is not particularly limited so long as contain the material of hydroxyl and get final product, and can utilize various resins.

As an example, can exemplify the cellulose-based polymer of Nitrocellulose, cellulose acetate, ethyl cellulose, carboxymethyl cellulose, methylcellulose gum etc., the synthetic macromolecule of butyral resin (polyvinyl butyral acetal (PVB)), polyvinyl alcohol, polyester polyol etc. etc.

Wherein, preferred butyral resin and ethyl cellulose, more preferably butyral resin.

These resins can use separately, perhaps mix or use as multipolymer.

In the manufacture method of the present invention, the containing ratio of glass powder in the slurry is not particularly limited, but take 20～90 % by weight (following brief note is as wt%) for well.

Containing ratio by making glass powder in the slurry is more than 20wt%, and a slurry coating just can be guaranteed enough thickness, can suppress repeatedly to be coated with to obtain the cost rising that required film thickness causes.On the other hand, the containing ratio by making glass powder in the slurry can prevent that the excess stickiness of slurry from increasing below 90wt%, can be well even coating sizing-agent.In addition, the containing ratio by making glass powder in the slurry can fully be guaranteed the amount of tackiness agent in the slurry below 90wt%, can obtain thus the filming of glass substrate 12 and slurry (below, sometimes with slurry film simply to be called film) between enough adaptations.

From above-mentioned some consideration, the containing ratio of glass powder is that 50～80wt% is better in the slurry.

On the other hand, the content of tackiness agent in the used slurry of manufacture method of the present invention also is not particularly limited, but with respect to 100 weight part frits, tackiness agent is that 1～50 weight part is better.

By make tackiness agent with respect to 100 weight part frits more than 1 weight part, can fully guarantee glass substrate 12 and film between adaptation.By make tackiness agent with respect to 100 weight part frits below 50 weight parts, can in pressurization operation described later, be coated with fully membrane rigidity, prevent from filming and on shaping dies, adhere to etc.In addition, by making tackiness agent below 50 weight parts, can reduce the space that produces because of unsticking mixture operation, and can after the glass powder firing process in reduce change of shape, can carry out with high precision more the shape control of lens section 14.

Consider above some, the amount of tackiness agent is that 5～30 weight parts are better with respect to 100 weight part glass powders in the slurry.

As previously mentioned, slurry forms this glass powder and tackiness agent dispersed/dissolved in solvent.Perhaps, be mixing forming after in the carrier as the mixture of tackiness agent and solvent, sneaking into glass powder.

Among the present invention, solvent is not particularly limited, can suitably determines according to used glass powder and tackiness agent.As an example, can use the hydro carbons such as toluene, dimethylbenzene, tetraline, the alcohols such as methyl alcohol, ethanol, the ketone such as acetone, methyl ethyl ketone, the ethers such as methylcyclohexane, ethyl cellosolve, ethylene glycol butyl ether, butyl carbitol, the ester such as methyl acetate, ethyl acetate class, glycols, the various organic solvents of Diethylene Glycol class etc.

In addition, except this composition, also can add as required for the tensio-active agent that improves coating or be used for adjusting pulp layer 20(and film in the slurry) softening agent of hardness etc.

Compound method to slurry is not particularly limited, for example, with solvent, glass powder and tackiness agent (or glass powder and carrier) or also have neccessary composition in addition to drop into mixing device or the kneading devices such as planetary-type mixer or roller pulverizer with specified amount, with the mode that the glass powder homogeneous disperses fully mix, mixing getting final product.

So, prepare glass substrate 12(Fig. 1 (A)), and preparation slurry (or prepare prepare in advance slurry) is coated slurry on the surface of glass substrate 12.

In the manufacture method of the present invention, the coating process of slurry is not particularly limited available various known coating processes.As an example, can exemplify that cylinder coating, hand are coated with, brushing, spin coating, dip-coating, silk screen printing, curtain are drenched, the coating processes such as rod is coated with, mould is coated with, intaglio plate be coated with, the coating of nick version, reverse roller coat, roller coat, flow coat, spraying, scraper for coating.

Wherein, owing to easy big area coating and once coating just can obtain the reasons such as adequate thickness, the use mould is coated with silk screen printing as well.

Perhaps, coated glass slurry and drying form and are raw cook on PET film etc., and raw cook hot pressing is received on the glass substrate 12, also can form pulp layer 20.

Here, as previously mentioned, in the manufacture method of the present invention, contain the boron oxide content of hydroxyl and glass powder by the tackiness agent that makes slurry below 40 % by mole, can guarantee the sufficiently long slurry life-span, therefore can be stably, well slurry is coated on the glass substrate 12.

The concaveconvex shape of the lens section 14 that the coating thickness of slurry can form according to the shape height of formed lens section 14, with aftermentioned shaping dies 24 etc. is suitably set.

For another example shown in Fig. 1 (B), slurry is coated on the surface of glass substrate 12 after, filming of slurry carried out drying (being desolventizing), become pulp layer 20.

Drying means to slurry is not particularly limited, such as using the method that the glass substrate 12 that has been coated with slurry is heated with baking oven, the method for UV irradiation etc.

Under the occasion of the dried coating film that makes slurry by heating, heating better under the temperature of tackiness agent stay-in-grade degree.

Film dry the time, it is thinner than the coating thickness of slurry that the bed thickness of pulp layer 20 can become, therefore consider at this moment dry after the bed thickness of pulp layer 20 of the gained coating thickness of setting aforementioned slurry for well.

So after the surface of glass substrate 12 forms pulp layer 20, then heating as required pulp layer 20 and making pulp layer 20(is tackiness agent in the pulp layer specifically) soften.

Heating means to pulp layer 20 are not particularly limited, and can use various known methods.About this point, be applicable to too unsticking mixture operation and firing process.

Be used for softening pulp layer 20 Heating temperature so long as more than the softening temperature of the tackiness agent of pulp layer 20, the specific viscosity mixture low temperature of temperature of decomposing, then be not particularly limited.That is to say, can suitably be set in the temperature that pulp layer 20 can enough shaping dies 24 extrusion formings after softening according to the kind of tackiness agent etc., but with 100～200 ℃ for well.

The heating process of this pulp layer 20 as described later, in the accompanying drawing example, is by pressurize to make the operation of pulp layer 20 before being configured as the operation of regulation shape (being mold pressing) with 24 pairs of pulp layers 20 of shaping dies.Here, the softening temperature by making pulp layer 20 is more than 100 ℃, and most of slurry of pulp layer 20 can be fully softening, and correctly being shaped becomes possibility.In addition, the softening temperature by making pulp layer 20 is below 200 ℃, and it is excessively softening to suppress the tackiness agent that causes because of excess Temperature, the decomposition of the tackiness agent that the adhering to of shaping dies, over-heating are produced that can prevent from well causing thus or rotten.

After pulp layer 20 is fully softening, shown in Fig. 1 (C)～Fig. 1 (D), use has the shaping dies 24 of press surface, this press surface is formed with corresponding with the shape of the male and fomale(M﹠F) of formed lens section 14 concavo-convex, by this to pulp layer 20 pressurize (pressing), then shown in Fig. 1 (D)～Fig. 1 (E), take off shaping dies 24 from pulp layer 20.

By this, can be with the shape mold pressing (being transfer printing) of shaping dies 24 to pulp layer 20 and be configured as the regulation shape corresponding with the male and fomale(M﹠F) of lens section 14.

Here, as previously mentioned, in the manufacture method of the present invention, contain the boron oxide content of hydroxyl and glass powder by the tackiness agent that makes slurry below 40 % by mole, guaranteed fully the slurry after glass substrate 12 and pulp layer 20(solvent are removed) between adaptation.

Therefore, when carrying out mold pressing with shaping dies 24, can in the situation that pulp layer 20 is not peeled off, be configured as well the regulation shape corresponding with the male and fomale(M﹠F) of lens section 14.

In this manufacture method, be not to directly forming with shaping dies after the glass substrate heating, but more soft pulp layer 20 is carried out press molding, by this can be with pressed temperature and pressure suppression at lower level, make pressurized conditions steadily (mild), therefore can in the situation that produces hardly expensive pressurizing mold loss, realize the long lifetime, have the glass member made of lens section with low cost fabrication.And, soft pulp layer 20 can be under lesser temps and lower pressure press molding, therefore can carry out very trickle shaping, be suitable for making and have the opticses such as trickle concavo-convex Fresnel lens or lens arra.

Release property between the plasticity of pulp layer 20 and pulp layer 20 and the shaping dies 24 (being separability) can be controlled by tackiness agent contained in the slurry, owing to do not rely on the material behavior of glass powder, so the material range of choice of glass powder is wide.

Formation material to shaping dies 24 is not particularly limited, so long as can give distortion that required dimensional precision, pulp layer 20 cause because of pressurization less, can keep required precision and material that the temperature during not because of pressurization soften or is gone bad, various materials all can use.

For example, can use metal, pottery etc.Specifically, can exemplify nickel or hardened steel as the material of metal die, can exemplify in addition pottery and burn till the various materials of using in the press molding mould of product.In addition, the material as ceramic die can exemplify silicon nitride, aluminum oxide, zirconium white etc.

Here, in the example shown in Figure 1, as shaping dies 24 illustrations flush type (impression type), but also can use well the sort of roll shape shaping dies that can carry out continuous molding shown in patent documentation 1 among the present invention.

Under the occasion of using roll shape, the load of shaping dies is concentrated and is wire, therefore can carry out continuously good shape transferred thereon with less load, and the demoulding is also easy.Its opposing face is under the occasion of using roll shape, and shaping dies is difficult to carry out for example two dimension of complexity processing as Fresnel lens.

On the other hand, under the occasion of using the flush type shaping dies, the whole applying load of essential effects on surface not only needs to apply more load according to the pressurization area, and the difficult demoulding of comparing with roll shape.Its reverse side is to carry out easily two dimension shaping processing.Its reverse side is than being easier to two dimension processing complicated as Fresnel lens.

Therefore, shaping dies 24 can come suitable choice for use roll shape or flush type according to the shape as the lens section 14 of target.

In the manufacture method of the present invention, in the operation of unsticking mixture described later, remove tackiness agent from pulp layer 20, after firing process in, the space that makes space that the glass powder welding exists with landfill and produce because of the unsticking mixture in pulp layer 20.

For this reason, for the pulp layer 20 that is shaped with shaping dies 24 generally, volumetric shrinkage is unavoidable.Therefore, must consider that the contraction that pulp layer 20 is carried out the shaping dies 24 of press molding designs its mold shape.

The pressure that pressurizes with shaping dies 24 is according to the material of slurry and difference, but with 10～80MPa for well.

By making moulding pressure more than 10MPa, the shape of shaping dies 24 can be transferred to effectively on the pulp layer, that is, obtain the shape transferred thereon of enough shaping dies.By making moulding pressure below 80MPa, can prevent well the glass substrate 12 that produces because of hypertonia or the breakage of shaping dies 12.Consider above-mentioned some, the pressure that pressurizes with shaping dies 24 is 10～50MPa more preferably.

Time with 20 pressurizations of 24 pairs of pulp layers of shaping dies also is not particularly limited, but preferred 10～120 seconds.

So pulp layer 20 usefulness shaping dies 24 are pressurizeed and after being shaped, then carry out removing from pulp layer 20 the unsticking mixture operation of tackiness agent.

Tackiness agent temperature in this unsticking mixture operation be in pulp layer tackiness agent can decompose more than the temperature of removing, than the low temperature of the second-order transition temperature of glass powder in the pulp layer, can suitably set according to the kind of tackiness agent, the second-order transition temperature of glass powder etc., but preferred 300～500 ℃.In addition, the time of unsticking mixture is according to the amount of tackiness agent in tackiness agent kind and the slurry and different, but preferred 5～60 minutes.

Moreover for promoting the oxygenolysis of tackiness agent, the unsticking mixture preferably carries out in air atmosphere.

So carry out then carrying out burning till of pulp layer 20 after the unsticking mixture, make the glass powder welding and form lens section 14, again glass substrate 12 is formed Fresnel lens 10 with lens section 14 weldings.

Firing temperature is more than the second-order transition temperature of glass powder in pulp layer, get final product than the low temperature of temperature of the softening temperature of glass substrate, can suitably set according to used glass powder, but preferably burn till under 350～650 ℃.

Firing atmosphere is also harmless under atmosphere, but discharges energetically outside the film for the bubble that will be present in the pulp layer, preferably under reduced pressure burns till.

Thus, can in lens section 14, not exist in the situation in bubble or space and obtain suitable and transparent high film at optics.

In the manufacture method of the present invention, preferably pulp layer 20 is heated to and keeps after the unsticking mixture temperature certain hour to carry out the unsticking mixture processing, reheat afterwards to firing temperature and keep certain hour to burn till, carry out the welding of glass powder.

But, the invention is not restricted to this, be to hold under the occasion of labile material there being tackiness agent for example, also can use following methods, namely, pulp layer 20 be shaped finish after with the temperature of pulp layer 20 gradually (or staged) rise to firing temperature, in the way that is heated to the firing temperature that causes the glass powder welding, finish the unsticking mixture.

Above example is with the manufacture method of glass member made of the present invention example for the manufacture of round Fresnel lens.But, the invention is not restricted to this, it can be applicable to make various glass member mades.

As described glass member made, preferably exemplify lens arra, diffuser plate, the inside that the substrate of microlens array, biconvex lens, prismatic lens, flat-panel monitor, surface have a male and fomale(M﹠F) shape has the various opticses such as diffuser plate, Polarizer that diffusion particle and surface have aforementioned various lens shapes, microreactor etc.

Fresnel lens or the lens arra that particularly can be applicable to the accompanying drawing example have trickle concavo-convex optics like that.

Example shown in Figure 1 is that pulp layer 20 is rear presses to make pulp layer 20 to become the example of the shape of lens section 14 with shaping dies to this pulp layer 20 by forming at glass substrate 12, namely forms the concavo-convex example of regulation shape by mold pressing.

But, the invention is not restricted to this, also can be having coating sizing-agent on the concavo-convex roller mould of regulation shape, behind the recess filling paste of this roller mould, slurry is transferred on the glass substrate from this roller mould, has the concavo-convex pulp layer of regulation shape in the formation of the surface of glass substrate by this.

That is to say, shown in the synoptic diagram of Fig. 4, prepare glass substrate 12(Fig. 4 (A)).

Also prepare to be formed with and the glass substrate 12 surperficial upward roller moulds 30 of the concavo-convex corresponding recess of the regulation shapes of formation.Coating sizing-agent on this roller mould 30, shown in Fig. 4 (B) behind the recess filling paste 34 of this roller mould 30, desolventizing.

Then, shown in Fig. 4 (C) like that, the roller mould 30 of having filled slurry 34 is pressed on the glass substrate 12, make the slurry 34 and glass substrate 12 crimping that are filled in recess, then roller mould 30 is taken off from glass substrate 12.By this, shown in Fig. 4 (D) like that, formed the regulation shape that is produced by pressurization on the surface of glass substrate 12 concavo-convex.

But, consider that from the aspects such as effect of the present invention that can present better adaptation excellence between described glass substrate and the slurry the present invention more preferably uses shown in Figure 1 passing through to carry out mold pressing and form the concavo-convex manufacture method of regulation shape that is produced by slurry at glass baseplate surface with shaping dies.

Such manufacture method of the present invention is not to directly being shaped with shaping dies after the glass substrate heating, be shaped but the more soft pulp layer that contains glass powder 20 pressurizeed, therefore cost is low, the selection degree of freedom of material and shape is high, big areaization realizes easily that also trickle concavo-convex shaping also becomes possibility.

Fig. 5 is used for synoptic diagram with an example of identical before round Fresnel lens with planar lens of the present invention.

Among Fig. 5, being the view of observing Fresnel lens from the optical axis direction of lens (A), (B) is the sectional view at the A-A line place of (A).

As shown in Figure 5, this Fresnel lens 40 is by glass substrate 42 be formed at the lip-deep optical function of this glass substrate 42 section 46 and consist of.

Optical function section 46 presents the position that makes the optical functions such as incident light refraction.In the accompanying drawing example, optical function section 46 has concavo-convex be used to the regulation shape that presents effect as Fresnel lens (namely being used for consisting of Fresnel lens).

In the Fresnel lens 40 as planar lens of the present invention, glass substrate 42 and optical function section 46 all are glass system, the pulp layer that comprises the glass powder that forms aforementioned optical function section is sintered on the glass substrate, by this not by binder layer etc. (namely not using tackiness agent etc.) directly welding engage.

Optical function section 46 as the jog of regulation shape consists of by forming different glass powders from glass substrate 42.This optical function section 46 is preferably formed by glass paste of the present invention.

Fresnel lens 40(planar lens of the present invention) in, the formation material of glass substrate 42 is not particularly limited, can uses various known glass.

Specifically, soda-lime glass etc. be can exemplify and alkali silicate glass, sapphire glass, alumina silicate glass etc. contained.

Here, in the Fresnel lens 40 of the present invention, the coefficient of expansion of the glass (being designated hereinafter simply as " glass substrate 42 ") that forms glass substrate 42 is not particularly limited, but the average coefficient of linear expansion under 50～350 ℃ (α) is 75 * 10 ^-7～100 * 10 ^-7/ ℃ better, 80 * 10 ^-7～85 * 10 ^-7/ ℃ good especially.

Fresnel lens 40 of the present invention has the optical function section 46 that the glass powder by the aftermentioned composition requirement forms.Optical function section 46 preferred uses glass paste of the present invention is made via firing process.Therefore, if the α between glass substrate 42 and the optical function section 46 is poor large, can produce the problems such as glass substrate 42 breaks when then burning till rear cooling.

Tg to glass substrate 42 also is not particularly limited, but preferably more than 530 ℃, more preferably more than 540 ℃.

As previously mentioned, Fresnel lens 40 is by namely having the concavo-convex pulp layer that forms for consisting of optical function section 46 to the 46(of optical function section) burn till and make.Firing temperature is set as low a little the temperature (for example Ts-20 ℃) of the Ts of the glass powder that is compared to optical function section 46 constituent materials for well, if but glass substrate 42 long-time heating then be out of shape easily under the high temperature more than 50 ℃ than Tg.Therefore, the Tg of glass substrate is preferably higher to prevent the substrate distortion.

As described later, the Ts of the glass of the optical function section of Fresnel lens of the present invention is typically 550～670 ℃, therefore firing temperature is typically 530～650 ℃, so the Tg of glass substrate 42 more than 530 ℃, be preferably 530 ℃～650 ℃, by this can be more effectively when making Fresnel lens 40, prevent well the deformation of glass substrate 42.

Glass substrate is the high glass substrate of weathering resistance for well.Moreover, the glass substrate with suitable basicity prevent and optical function section between peel off aspect better.

The α of soda-lime glass commonly used is 85 * 10 ^-7～90 * 10 ^-7/ ℃ about, Tg is about 550 ℃.In addition, the α that is used for the high strain-point glass of display base plate etc. is 80 * 10 ^-7～90 * 10 ^-7/ ℃ about, Tg is about 600～650 ℃.

Having excellent weather resistance of these glass, and the binding property between the optical function section is also good.

Therefore, among the present invention, can utilize well soda-lime glass, the such glass substrate commonly used 42 of high strain-point glass.

As previously mentioned, the Fresnel lens 40 as planar lens of the present invention has optical function section 46 at such glass substrate 42.This optical function section 46 is the positions that mainly present optical effect in Fresnel lens 40.

Here, this optical function section 46 forms by forming different glass from glass substrate 42.In addition, optical function section 46 by contain following component and not the glass powder of bismuth-containing compound, lead compound and phosphorus compound form, with the oxide compound benchmark % by mole the expression a described component be respectively: silicon oxide (SiO ₂) 40～64%, boron oxide (B ₂O ₃) 5～35%, zinc oxide (ZnO) 2～30%, aluminum oxide (Al ₂O ₃) 1～10%, Lithium Oxide 98min (Li ₂O), sodium oxide (Na ₂O) and potassium oxide (K ₂O) at least a adds up to 10～22%, and barium oxide (BaO) and at least a of strontium oxide (SrO) add up to 0～10%.

The present invention is by having this formation, even can be easy and planar lens that easily the stable planar lens that obtains the complicated shape as Fresnel lens 40 so also has the good whole glass system of required shape and the transparency.

To comprise glass powder, tackiness agent and solvent as feature, wherein glass powder comprises following composition with % by mole expression of oxide compound benchmark to glass paste of the present invention: silicon oxide (SiO as mentioned above ₂) 40～64%, boron oxide (B ₂O ₃) 5～35%, zinc oxide (ZnO) 2～30%, aluminum oxide (Al ₂O ₃) 1～10%, Lithium Oxide 98min (Li ₂O), sodium oxide (Na ₂O) and potassium oxide (K ₂O) at least a adds up to 10～22%, and at least a of barium oxide (BaO) and strontium oxide (SrO) is 0～10%.

Form in the glass (following also referred to as " optical function section 46 ") of optical function section 46, silicon oxide is the essential composition that consists of the glass skeleton, and its content % by mole represents that (following omission " take % by mole expression of oxide compound benchmark ") is as 40～64% with the oxide compound benchmark.

As described later, Fresnel lens 40(planar lens of the present invention) preferably makes in the same manner with the manufacture method of aforesaid glass member made of the present invention, that is, the layer of coating glass paste of the present invention on the glass substrate is carried out mold pressing and become optical function section 46 shape, burn till, the integrated optical function of formation and glass substrate 42 section 46.Here, if the content of silicon oxide less than 40%, the shape-holding property when then burning till can have low anxiety.Also have α that the anxiety that becomes large is arranged.Conversely, if the content of silicon oxide surpasses 64%, then Ts uprises.

The content of silicon oxide is preferably more than 43%, more preferably more than 50%, in addition preferably below 62%.

5～35% boron oxide is contained in optical function section 46.Boron oxide is the composition of the effect of the effect with the stabilization of making, the difference that increases Ts and Tg etc., therefore is essential composition.

As previously mentioned, " Ts-Tg " large glass is then weak few, before burning till and the shape-holding property after burning till excellent.Therefore, by using the glass paste that is consisted of by " Ts-Tg " large glass, can be with the optical function section 46 of good accurate manufacturing technique desired shape.

The content of boron oxide then has the anxiety of above-mentioned effect deficiency less than 5%.Conversely, if the content of boron oxide surpasses 35%, the anxiety of water tolerance reduction is arranged then.In addition, have the storage stability (slurry life-span) of glass paste not enough, glass paste is to the anxiety of the adaptation deficiency of substrate.Also have the unsticking mixture performance of glass paste low, burn till glass substrate and the anxiety of transparency deficiency of optical function section.Moreover, there is the situation of the shape-holding property deficiency in the firing process.

The content of boron oxide is preferably more than 8%, in addition preferably below 18%.

2～30% zinc oxide is contained in optical function section 46.Zinc oxide is the composition that has the effect, the effect that reduces α that reduce Ts, makes the effect of stabilization etc., is essential composition.

If the content of zinc oxide is less than 2%, then above-mentioned effect is insufficient.If the content of zinc oxide surpasses 30%, the easy crystallization of glass in the firing process then has the anxiety of transparent reduction.In addition, there is the low situation of chemical durability, particularly acid resistance.

The content of zinc oxide is preferably more than 4%.

1～10% aluminum oxide is contained in optical function section 46.Aluminum oxide is the composition of the effect of the effect that to improve chemical durability, increase " Ts-Tg " etc., is essential composition.

The content of aluminum oxide is preferably below 10%.If the content of aluminum oxide surpasses 10%, then produce sometimes the unfavorable conditions such as the unsticking mixture of glass paste is deteriorated.

More than one that add up to 10～22% Lithium Oxide 98min, sodium oxide and potassium oxide are contained in optical function section 46.Lithium Oxide 98min, sodium oxide and potassium oxide all are the compositions that makes the melt temperature decline of glass or reduce Ts, and more than one are essential composition arbitrarily.On the contrary, Lithium Oxide 98min, sodium oxide and potassium oxide also are the compositions that increases α, reduces Ts-Tg.

If the content of Lithium Oxide 98min, sodium oxide and potassium oxide adds up to less than 10%, then can produce the Ts high rough sledding that became.And if the total amount of these three kinds of compounds surpasses 22%, then there is α to become excessive and the anxiety of the shape-holding property deficiency when burning till.

The content of these three kinds of compounds adds up to preferably below 20%, more preferably below 18%.

Here, optical function section 46 contain sodium oxide or potassium oxide both one of or all contain promising good.

If any of oxygen-freeization sodium, potassium oxide namely only contains lithium as alkali metal component, then when glass substrate 42 burnt till, glass substrate produced warpage easily.Think that this is owing to the cause that the basic ion exchange has occured between the glass contained in glass substrate in the firing process and the glass paste.That is to say, the glass substrate 42 that uses among the present invention contains sodium oxide or potassium oxide as the alkali composition under most of occasions, therefore owing to the ion-exchange between the little lithium ion of basic ion contained in the glass substrate 42 and ionic radius deforms glass substrate 42.

Consider that from above aspect the content of Lithium Oxide 98min is preferably below 15% in the optical function section 46.

Among the present invention, various compositions also can be contained in optical function section 46 except above-mentioned essential composition.

For example, as the composition of adjusting specific refractory power, can contain barium oxide or strontium oxide both one of or all contain.

When containing barium oxide and strontium oxide, its content is not particularly limited, but adds up to preferably below 10%.If both content surpasses 10%, the anxiety that then has glass to become unstable.The anxiety that also has Ts-Tg to diminish.The content of barium oxide and strontium oxide is preferably below 5%.

In addition, as the effect that can obtain to increase " Ts-Tg ", improve the composition of the effect of water tolerance etc., can contain zirconium white.

When containing zirconium white, its content is not particularly limited, but preferably below 5%.If zirconic content surpasses 5%, the anxiety that then has Ts to become too high.The anxiety that also has the easy crystallization of glass.

In addition, as the effect that can obtain to improve water tolerance, improve the composition of the effect of the transparency etc., can contain one of stannic oxide and cerium oxide or all contain.

When containing stannic oxide or cerium oxide, its content is not particularly limited, but preferably below 5%.If the content of stannic oxide and cerium oxide surpasses 5%, the anxiety that then has Ts to become too high.The anxiety that also has the easy crystallization of glass.

As previously mentioned, Fresnel lens 40(planar lens of the present invention) in, optical function section 46 except the situation of the impurity that contains inevitably each material composition that comes from the used glass ingredient of the glass of making above-mentioned composition, in fact not bismuth-containing compound, lead compound and phosphorus compound.

Among the present invention, owing to do not contain these compositions, even can simple and easy and stably make the planar lens that as Fresnel lens, has complex construction or have the lens that the planar lens of fine structure also has required shape and has excellent transparency.

If bismuth compound is contained in optical function section 46, then " Ts-Tg " reduces.Shape-holding property when consequently burning till is significantly deteriorated, can not make the optical function section 46 with desired shape.Particularly for the planar lens with complicated shape as the Fresnel lens of accompanying drawing example, its detrimentally affect is very large.In addition, if contain bismuth compound, then glass is painted easily, therefore also has the deteriorated situation of the transparency.

Moreover if phosphorus compound is contained in optical function section 46, then the unsticking mixture of glass paste described later declines to a great extent, and perhaps easily because burning till crystallization, is difficult to obtain the excellent Fresnel lens of the transparency.

In addition, optical function section 26 is for the consideration of environment countermeasure aspect, not lead-containing compounds.

Fresnel lens 40(planar lens of the present invention) in, the Tg with optical function section 46 of above-mentioned composition typically is 450～550 ℃.

If the Tg of optical function section is less than 450 ℃, the fusion temp of unsticking mixture temperature and glass powder approaches when then burning till, and the fully anxiety of unsticking mixture is arranged.If the Tg of optical function section surpasses 550 ℃, then be used to form the required firing temperature of optical function section and raise, the anxiety of substrate distortion is arranged when burning till.

In addition, the Ts of optical function section 46 typically is 550～670 ℃.Here, under the occasion of glass substrate 42 for soda-lime glass commonly used, the Ts of the glass of optical function section 46 is preferably below 640 ℃, more preferably below 630 ℃.In addition, preferably the Tg than glass substrate 42 is low for the Ts of optical function section 46.

In addition, Ts refers to the bottom temperature (Japanese: full front of a Chinese gown temperature) of the second endothermic section of differential thermal analysis (DTA) curve.

Among the present invention, the Ts by making optical function section 46 can realize in glass substrate 42 indeformable situations that the practical aspect such as burn till obtains better result in above-mentioned scope.

Herein, " Ts-Tg " of optical function section 46 is not particularly limited, but preferably more than 110 ℃.

As previously mentioned, " Ts-Tg " large glass, the weakness in the time of suppressing to burn till and the optical function section 46 that makes desired shape.By making " Ts-Tg " more than 110 ℃, the shape-holding property when burning till after can keeping well glass paste to be shaped.In addition, consider that from the angle that obtains better this effect " Ts-Tg " of the glass of optical function section 46 is more preferably more than 120 ℃.

Moreover the α of optical function section 46 typically is 70 * 10 ^-7～85 * 10 ^-7/ ℃ better.In addition, the α of optical function section 46 is than the slightly little strength degradation of glass substrate 42 thereby comparatively desirable that then can not make of α of glass substrate 42.Particularly under glass substrate 42 occasion for soda-lime glass commonly used, the α of optical function section 46 more preferably 72 * 10 ^-7～82 * 10 ^-7/ ℃.

Among the present invention, the α by making optical function section 46 in above-mentioned scope, this α can reach with the glassy phase commonly used such as soda-lime glass with level.In addition, also can be slightly less than the α of glass substrate 42.Consequently, even during as glass substrate 42, also can prevent the poor stress that causes because of α with glass commonly used, thereby the deformation that prevents from being caused by this stress, and glass substrate 42 and optical function section 46 between peel off etc.

In addition, the α by making glass substrate 42 is above-mentioned 75 * 10 ^-7～100 * 10 ^-7/ ℃ scope in, the α that can dwindle between glass substrate 42 and the optical function section 46 is poor.Thus, can be at the poor stress that causes of the α that prevents both, prevent that the aspect such as peel off between cracking and the deformation that is caused by this stress, the strength degradation that prevents glass substrate 42 and glass substrate 42 and the optical function section 46 from obtaining better result.

Fresnel lens 40(planar lens of the present invention) in, has the glass and the glassy phase ratios commonly used such as soda-lime glass of the optical function section 46 of this composition, have enough low Ts, also have the α of par.Therefore, even under the occasion of the glass substrate 42 that uses glass system commonly used, also can form optical function section 46 at glass substrate 42 by burning till.

When making described planar lens, at first will form composition contained in the glass of optical function section 46 and pulverize and make glass powder, and carrier be mixed with glass powder or solvent mixed with tackiness agent with glass powder and prepare slurry (glass paste).Then, by burning till at coating sizing-agent on the glass substrate 42, after making the gained pulp layer be configured as the shape corresponding with the shape of the optical function section 46 that stipulates, can under the situation of significantly distortion does not occur glass substrate 42, not make high optical function section 46 driving fits of transparency and be formed on the glass substrate 42.

The shape of optical function section can be come that pulp layer is carried out die forming and forms by be formed with concavo-convex shaping dies of required regulation etc. such as use.But pulp layer can because burning till volumetric shrinkage, therefore, must consider that shrinkage designs shaping dies.

The below quotes the schema of above-mentioned Fig. 1 and Fig. 2, and the preferable production process of the Fresnel lens 40 of an embodiment of planar lens of the present invention is elaborated.

That is to say that Fresnel lens of the present invention can preferably be used based on the method for the manufacture method of the glass member made of the invention described above and make.

As previously mentioned, in the Fresnel lens 40 of the present invention, the preferred glass paste of the present invention (in the following explanation, glass paste is also referred to as slurry) that contains glass powder that utilizes forms optical function section 46.

Glass powder can pulverize by the frit that will contain above-mentioned silicon oxide, boron oxide, zinc oxide etc., make powder by usual method makes.

Specifically, the mode of following composition is modulated so that the composition of the glass powder of gained contains, mixing raw material: silicon oxide 40～64%, boron oxide 5～35%, zinc oxide 2～30%, aluminum oxide 0～10%, the at least a of Lithium Oxide 98min, sodium oxide and potassium oxide adds up to 10～22%, and at least a of barium oxide and strontium oxide adds up to 0～10%.

This mixture is dropped into melting behind the thermally resistant container of crucible etc., then cool off and obtain glass.

Then, this glass is pulverized and made powder with known approaches such as mortar, ball mill, jet mills, carry out as required classification, make the glass powder that forms optical function section 46.At this moment, also can come modifying surface to above-mentioned glass powder with tensio-active agent or silane coupling agent.

In addition, the equal particle diameter of the matter of glass powder is preferably 0.1～10 μ m.

More than 0.1 μ m, the easy homogeneous of glass powder is scattered in the slurry by the equal particle diameter of the matter that makes glass powder.By the equal particle diameter of the matter that makes glass powder below 10 μ m, the surface smoothness after can being coated with well or burning till.Moreover the shaping of being undertaken by shaping dies etc. also can be stablized and easily be implemented.

Slurry usually by with glass powder and carrier (being glass powder and tackiness agent and solvent), also have as required in addition composition to make it the homogeneous dispersion with mixing such as planetary stirring machine, roller pulverizers to obtain.As previously mentioned, carrier is that tackiness agent and solvent form.Carrier is mixed into respect to the ratio of 100 weight part glass powders as 3～50 weight parts take tackiness agent.

As tackiness agent, can use the various resins such as ethyl cellulose, Nitrocellulose, acrylic resin, vinyl-acetic ester, butyral resin (polyvinyl butyral acetal (PVB)), Resins, epoxy.

Wherein, the preferred resin with (end) hydroxyl that uses particularly preferably uses butyral resin.

In the explanation of the manufacture method of aforesaid glass member made of the present invention, state, in the manufacture method of Fresnel lens 40 of the present invention, form pulp layer 50 at glass substrate 42, press with 24 pairs of pulp layers 50 of shaping dies, pulp layer 50 form make concavo-convex that required optical function brought into play after, shaping dies 24 is taken off, and mold pressing goes out the shape of optics function part 46.Therefore, pulp layer 50 is required to have and glass substrate 12 between adaptation.In addition, slurry does not directly use afterwards in preparation, therefore requires the slurry life-span long.

As previously mentioned, for guaranteeing the good adaptation between glass substrate 42 and the glass paste, must use butyral resin etc. to contain the tackiness agent of hydroxyl.But, contain at glass powder under the occasion of boron oxide, there is the situation that can not obtain enough slurries life-span because of the specific reaction between boron oxide and the hydroxyl, the adaptation between glass substrate 42 and the slurry is also low.

To this, the content by making boron oxide in the slurry of the present invention has been realized guaranteeing the adaptation between glass substrate 42 and the glass paste and has been obtained the sufficiently long slurry life-span below 35%.

That is to say, in the Fresnel lens 40 of the present invention, glass powder by will having aforementioned composition requirement and butyral resin etc. have the binder combination of hydroxyl, can satisfy adaptation between adaptation between glass substrate 12 and the tackiness agent excellent and glass powder and the tackiness agent low preferably be considered to opposite characteristic.Thus, realize that simultaneously adaptation and long slurry life-span between glass paste and the glass substrate 42 become possibility.

The solvent of carrier is the solvent of dissolved adhesive.

Solvent is not particularly limited, but can use toluene, dimethylbenzene, ethanol, butanols, pentyl acetate, α-terpinol, 2-(2-n-butoxy oxyethyl group) ethanol, acetic acid 2-(2-n-butoxy oxyethyl group) ethyl ester, 2,2,4-trimethylammonium-1, the organic solvents such as 3-pentanediol mono isobutyrate also can suitably will use after these solvent.

In addition, except above-mentioned glass powder and carrier, also can contain as required softening agent or dispersion agent etc. in the glass paste, this manufacture method with aforesaid glass member made of the present invention is identical.

Prepared after glass substrate 42 and the slurry, shown in Fig. 1 (A)～(B), coating sizing-agent and make it dry (desolventizing) and become pulp layer 50 on the surface of glass substrate 42.

The coating of pulp layer and dry can similarly carrying out with the occasion of the pulp layer 20 of the manufacture method of aforesaid glass member made of the present invention.

Formed after the pulp layer 50, shown in Fig. 1 (C)～(D), with having the concavo-convex shaping dies 24(mould corresponding with the shape of formed optical function section 46) pulp layer 50 is pressed (pressurization), form concaveconvex shape at pulp layer, then shown in Fig. 1 (D)～(E), take off shaping dies 24 from pulp layer 20.

Thus, the shape of shaping dies 24 can be pressed (transfer printing) to pulp layer 20 and form the regulation shape corresponding with the male and fomale(M﹠F) of optical function section 46.In addition, use at slurry under the occasion of the tackiness agent with hydroxyl, can fully guarantee between glass substrate 42 and the pulp layer 50 adaptation, prevent from making in the situation that pulp layer 20 peels off pulp layer 50 to be configured as the suitable shape corresponding with optical function section 46.

Formation material to shaping dies 24 is not particularly limited, and can use the material identical with aforesaid manufacture method of the present invention.Moulding pressure also with before identical, is generally 10～80MPa, preferably below 50MPa.

In addition, shaping dies is not limited to the sort of flush type (impression type) of accompanying drawing example, also can suitably use the roll shape shaping dies, and this manufacture method with aforesaid glass member made of the present invention is identical.

Moreover in this manufacture method, the volumetric shrinkage of pulp layer 50 is unavoidable in the firing process thereafter, so shaping dies 24 must consider that it shrinks the designing mould shape, and also the manufacture method with aforesaid glass member made of the present invention is identical for this.

In addition, identical with aforesaid manufacture method of the present invention, better be before pressing with shaping dies 24, pulp layer 50 suitably to be heated and make pulp layer 50(tackiness agent) softening to improve shaping processability.

The heating means of pulp layer 50 and Heating temperature can be prepared according to the manufacture method of aforesaid glass member made of the present invention.

Form thus after the pulp layer 50, by pulp layer 50 is burnt till to form optical function section 46.

This burn till be make the glass powder of pulp layer 50 softening by being heated to temperature with the Ts same degree of glass powder of the present invention/be cooled to room temperature after the welding to be bonded to operation on the glass substrate 42.Thus, form optical function section 46 on the surface of glass substrate 10, made the Fresnel lens 40(planar lens of the present invention of whole glass system).

In the firing process, keep certain temperature (firing temperature) to cool off afterwards after normally temperature rises.Hold-time is identical with the manufacture method of aforesaid glass member made of the present invention, is generally 30～60 minutes.

In addition, Fresnel lens 40(planar lens of the present invention) in the manufacturing, firing temperature for well, particularly preferably hangs down about 5～50 ℃ low temperature than Ts near the Ts of the glass powder that forms optical function section 46.Therefore, in the manufacturing of Fresnel lens of the present invention, firing temperature usually with 540～630 ℃ for well.

Here, before firing process, carry out the foregoing tackiness agent of carrier that makes and decompose the unsticking mixture operation that disappears.Perhaps, also can comprise unsticking mixture operation in firing process, this unsticking mixture operation is to remain on than the tackiness agent that makes carrier under the low temperature of the Tg of glass to decompose disappearance before reaching firing temperature.When the contained tackiness agent of glass paste was butyral resin, unsticking mixture operation for example was 300～500 ℃ of lower operations that keep 5～60 minutes.Perhaps, also can be warming up in the way of firing temperature in continuous or staged, control temperature in the firing process in the mode of finishing the unsticking mixture, also the manufacture method with aforesaid glass member made of the present invention is identical for this.

Unsticking mixture operation is carried out under air atmosphere usually.But the firing process behind the unsticking mixture under reduced pressure carries out as previously mentioned sometimes.Burn till by reducing pressure, the space that pulp layer is contained and bubble collapse can obtain the higher optical function section of the transparency.

Above example is the example that utilizes planar lens of the present invention and glass paste at the round Fresnel lens of the stroboscopic lamp of the beam condensing unit that is suitable for solar cell and digital camera etc.But, the invention is not restricted to this, it can be applicable to various planar lenss.

What for example, exemplify preferably that one dimension extends is concavo-convexly arranging the various planar lenss such as the Fresnel lens (Fresnel lens of line style) that forms, lens arra, microlens array, biconvex lens, prismatic lens with the direction of bearing of trend quadrature.

Particularly, the manufacture method of glass member made of the present invention and glass paste Fresnel lens and the lens arra that can be applicable to make the accompanying drawing example has trickle concavo-convex optics like that.

More than the manufacture method of glass member made of the present invention and planar lens and glass paste are had been described in detail, but the present invention is not limit by above-mentioned example obviously, can carry out various improvement or change in the scope that does not deviate from aim of the present invention.

Embodiment

The below enumerates specific embodiments of the invention, and the present invention will be described in more detail.The invention is not restricted to this.

Embodiment 1

[example 1]

Preparing boron oxide content is 10.5 % by mole (11 % by weight), Tg(softening temperature) be 503 ℃, Ts(second-order transition temperature) be the glass powder (SiO of 638 ℃ (Ts-Tg=135 ℃) ₂-B ₂O ₃-ZnO is glass).

20 weight part butyral resins (carat MowitalB30HH processed of Thunder God department (Network ラ レ society of Co., Ltd.)) are dissolved in 80 parts by weight solvent (butyl carbitol acetic ester), make carrier (binder solution).This glass powder of 100 weight parts and 100 weight part carriers are dropped into mixing tank, fully stir the formulate glass slurry.

As glass substrate 12, prepare the square soda-lime glass (thermal expansivity 85 * 10 of 140mm ^-7/ ℃, 735 ℃ of softening temperatures, 550 ℃ of second-order transition temperatures).

Metal mask at these glass substrate 12 use mask thickness 200 μ m is coated with the slurry for preparing by silk screen print method.In addition, glass substrate 12 coating sizing-agents are carried out in 60 minutes behind slurry preparation.

Afterwards, the glass substrate that has been coated with slurry is dropped into drying machine, drying is 40 minutes under 180 ℃, and acquisition is formed with the glass substrate 12 of the pulp layer 20 of thick 200 μ m.

The glass substrate 12 that will be formed with above-mentioned pulp layer 20 is arranged on the press that platform is heated to 200 ℃, load at pulp layer 20 and to be formed with the concavo-convex plane shaping dies corresponding with round Fresnel lens shown in Figure 3 (nickel system, square, the lens height 150 μ m of size 140mm), glass substrate 12 applied pressures are carried out 60 seconds pressurization as the mode of 50MPa.

Afterwards, with the shaping dies demoulding, the pulp layer 20 of shaping dies shape (being lens section 14) that obtained mold pressing.

To be formed with mold pressing the glass substrate 12 of pulp layer 20 of shaping dies shape drop into firing furnaces, the heat-up rate with 5 ℃/minute in air atmosphere is warming up to 450 ℃, 450 ℃ of lower maintenances 90 minutes, carries out the unsticking mixture.

Then, by firing furnace being decompressed to 100Pa, being warming up to 620 ℃, burning till in 30 minutes 620 ℃ of lower maintenances with 5 ℃/minute heat-up rates, carry out the welding of glass powder, obtain as shown in Figure 3 glass substrate 12 and the lens section 14 direct Fresnel lenses 10 that engage.

[example 2]

Preparing boron oxide content and be 12.6 % by mole of (14 % by weight), Tg and be 485 ℃, Ts is the glass powder (SiO of 606 ℃ (Ts-Tg=121 ℃) ₂-B ₂O ₃-Al ₂O ₃Be glass).

Except glass powder being changed to this glass powder, fundamental sum example 1 is made Fresnel lens 10 in the same manner.

In addition, burn till by firing furnace being decompressed to 100Pa, being warming up to 580 ℃, carrying out in 30 minutes 580 ℃ of lower maintenances with 5 ℃/minute heat-up rates.

[example 3]

Preparing boron oxide content and be 13 % by mole of (14 % by weight), Tg and be 500 ℃, Ts is the glass powder (SiO of 635 ℃ (Ts-Tg=135 ℃) ₂-B ₂O ₃-Al ₂O ₃Be glass).

Except glass powder being changed to this glass powder, fundamental sum example 1 is made Fresnel lens 10 in the same manner.

In addition, burn till by firing furnace being decompressed to 100Pa, being warming up to 600 ℃, carrying out in 30 minutes 600 ℃ of lower maintenances with 5 ℃/minute heat-up rates.

[example 4]

Preparing boron oxide content and be 13.9 % by mole of (13 % by weight), Tg and be 506 ℃, Ts is the glass powder (SiO of 615 ℃ (Ts-Tg=109 ℃) ₂-B ₂O ₃-Al ₂O ₃Be glass).

Except glass powder being changed to this glass powder, fundamental sum example 1 is made Fresnel lens 10 in the same manner.

In addition, burn till by firing furnace being decompressed to 100Pa, being warming up to 600 ℃, carrying out in 30 minutes 600 ℃ of lower maintenances with 5 ℃/minute heat-up rates.

[example 5]

Preparing boron oxide content and be 19.6 % by mole of (20.5 % by weight), Tg and be 584 ℃, Ts is the glass powder (SiO of 759 ℃ (Ts-Tg=175 ℃) ₂-B ₂O ₃-BaO is glass).

Except glass powder being changed to this glass powder, and example 1 obtains being formed with the glass substrate 12 of the pulp layer 20 of thick 200 μ m in the same manner.

The softening temperature of this glass powder is higher than soda-lime glass, does not therefore carry out making and the shape-holding property evaluation described later of Fresnel lens 10, only slurry life-span and adaptation is estimated.

[example 6]

Preparing boron oxide content and be 38.9 % by mole of (35 % by weight), Tg and be 477 ℃, Ts is the glass powder (SiO of 591 ℃ (Ts-Tg=114 ℃) ₂-B ₂O ₃-BaO is glass).

Except glass powder being changed to this glass powder, fundamental sum example 1 is made Fresnel lens 10 in the same manner.

In addition, burn till by firing furnace being decompressed to 100Pa, being warming up to 580 ℃, carrying out in 30 minutes 580 ℃ of lower maintenances with 5 ℃/minute heat-up rates.

[example 7]

With 20 weight part ethyl cellulose resins ((ハ ー キ ュ レ ス society of Hercules company) EC-N7 processed) be dissolved in 80 parts by weight solvent (butyl carbitol acetic ester), make carrier.

Except carrier being changed to this carrier, and example 1 is prepared (glass powder) slurry in the same manner.

Obtain in the same manner to be formed with the glass substrate 12 of the pulp layer 20 of thick 200 μ m with example 1.Then, except platform temperature is changed to 140 ℃, and example 1 is pressurizeed in the same manner.

Afterwards, with the shaping dies demoulding, under the firing condition identical with example 1, burn till, make Fresnel lens 10.

[comparative example 1]

Preparing boron oxide content and be 46 % by mole of (46.5 % by weight), Tg and be 475 ℃, Ts is the glass powder (SiO of 583 ℃ (Ts-Tg=108 ℃) ₂-B ₂O ₃-ZnO is glass).

Except glass powder being changed to this glass powder, fundamental sum example 1 is made Fresnel lens 10 in the same manner.

In this example, when the shaping dies in the operation of will pressurizeing took off, pulp layer was peeled off from glass substrate, the operation after therefore can not carrying out.

[comparative example 2]

Preparing boron oxide content and be 46.3 % by mole of (47.4 % by weight), Tg and be 476 ℃, Ts is the glass powder (SiO of 580 ℃ (Ts-Tg=104 ℃) ₂-B ₂O ₃-ZnO is glass).

Except glass powder being changed to this glass powder, fundamental sum example 1 is made Fresnel lens 10 in the same manner.

In this example, when the shaping dies in the operation of will pressurizeing took off, pulp layer 20 was peeled off from glass substrate 12, the operation after therefore can not carrying out.

[comparative example 3]

Preparing boron oxide content and be 46.9 % by mole of (45.6 % by weight), Tg and be 466 ℃, Ts is the glass powder (SiO of 563 ℃ (Ts-Tg=97 ℃) ₂-B ₂O ₃-BaO is glass).

Except glass powder being changed to this glass powder, fundamental sum example 1 is made Fresnel lens 10 in the same manner.

Burn till by being decompressed to 100Pa in the firing furnace, being warming up to 550 ℃, carrying out in 30 minutes 550 ℃ of lower maintenances with 5 ℃/minute heat-up rates.

[comparative example 4]

With 20 parts by weight of acrylic acid resins (the (ロ ー of Rohm ﹠ Haas Corp system ア Application ド ハ ー ス society) ParaloidA-21 processed) be dissolved in 80 parts by weight solvent (butyl carbitol acetic ester), make carrier.

Except carrier being changed to this carrier, and example 1 formulate glass slurry in the same manner.

Obtain in the same manner to be formed with the glass substrate 12 of the pulp layer 20 of thick 200 μ m with example 1.Then, except platform temperature is changed to 120 ℃, and example 1 is pressurizeed in the same manner.

In this example, when the shaping dies in the operation of will pressurizeing took off, pulp layer 20 was peeled off from glass substrate 12, the operation after therefore can not carrying out.

[evaluation]

To such example 1～example 7 and comparative example 1～comparative example 4, carry out the adaptation between slurry life-span, glass substrate 12 and the pulp layer 20 and burn till before and after the evaluation of change of shape (shape-holding property).

Evaluation method is as described below.

[slurry life-span (below be also referred to as the life-span)]

Prepare behind the slurry and minute to get a part, with the unvaporized mode encloses container of solvent, at room temperature preserve, estimate the slurry life-span.

Estimate following carrying out.

◎: unchanged more than one month

Zero: one week is above unchanged

△: became glue, and can not be coated with in about one day

*: become glue in several hours, can not be coated with.

[adaptation]

Slurry desolventizing on coating glass substrate 12 and forming after the pulp layer 20, the surface of pressing pulp layer 20 with the pressure of 0.4MPa with the roller (surface nickel system) of radius 60mm on one side, on one side with 30mm/ minute speed movable glass substrate 12, last 1 minute, then take off roller, estimate.

Estimate following carrying out.

◎: have no pulp layer fully and peel off from glass substrate.

Zero: float though see that pulp layer slightly has, be unlikely to peel off, actual use upper no problem.

△: some peels off pulp layer, but overburden amount is less than half.

*: pulp layer has over half peeling off.

[shape-holding property]

Compare by the shape to the lens section 14 before and after burning till, estimate shape-holding property.

Estimate following carrying out.

◎: the lens height after burning till is more than 50% of lens height before burning till.

Zero: the lens height after burning till be before burning till lens height more than 20% less than 50%.

△: the lens height after burning till be before burning till lens height more than 10% less than 20%.

*: the lens height after burning till is less than 10% of the lens height before burning till.

In addition, as previously mentioned, comparative example 1 and 2 pulp layer when the pressurization operation is peeled off from glass substrate, therefore can not carry out the shape-holding property evaluation.

More than the results are shown in following table 1.

Table 1

As above shown in the table 1, use the example 1～7 of manufacture method of the present invention on slurry life-span, adaptation and shape-holding property, all to obtain good result.Particularly " Ts-Tg " obtained excellent shape-holding property in the example 1～3,7 more than 120 ℃.

In addition, although boron oxide content is that 46.9 % by mole comparative example 3 presents good adaptation in the glass powder, but think this be since certain reason so that the reaction between tackiness agent and the frit is slow, only after slurry just makes namely under the occasion of coating fully existence can with the reason of the OH base of glass substrate reaction etc.But the slurry life-span of comparative example 3 is short, and thinking extremely difficult provides in Practical manufacturing.

Embodiment 2

[the making transitivity of glass powder is estimated]

With raw material modulation, mix, to form table 2(sample 1～sample 8) and table 3(sample 9～sample 14) shown in the glass composition.

Composition is with the mole expression of oxide compound benchmark.In addition, the sample 1～8th shown in the table 2, the glass corresponding with planar lens of the present invention and glass paste forms, the sample 9～14th shown in the table 3, not corresponding with the present invention glass forms (comparative example).

This mixing raw material is heated to 1400 ℃ with platinum alloy crucible respectively made it melting 60 minutes.

Make the part of the melten glass of gained flow into respectively stainless steel roller to form thin slice.This glass flake after 12 hours, is removed the coarse grain that surpass 8 μ ms by air classification with the pulverizing of oxidation aluminum ball mill, obtain D ₅₀It is the glass powder of 2～4 μ m.

As sample, use differential thermal analysis device (DTA) to measure the Tg(second-order transition temperature of each glass the glass powder of this sample 1～14) and the Ts(softening temperature).

Make remaining melten glass flow into stainless steel molding box processed, Xu Leng.Cylindric with part processing growth 20mm, the diameter 5mm of the glass of Xu Lenghou, the dilatometer of usage level differential detection mode (TD5010SA-N processed of Brooker AXS company (Block Le カ ー エ イ エ ッ Network ス エ ス society)) is measured the α (average coefficient of linear expansion) of the glass of sample 1～14.In addition, standard material uses silica glass.

The Tg of each glass, Ts and Ts-Tg(unit: ℃) and α (unit: 10 ^-7/ ℃) charge in the lump table 2 and table 3.In addition, the result of sample 6～8 forms the guess value of inferring from glass.

Table 2

Table 3

[making of planar lens]

Use sample 1～3(in such sample 1～14 corresponding with the present invention) and sample 9～14(comparative example) each glass powder, make Fresnel lens shown in Figure 5.

At first, with 20 weight part tackiness agents (butyral resin: carat Thunder God MowitalB30HH processed of department) be dissolved in 80 weight parts (butyl carbitol acetic ester), formulation vehicle.

This carrier of 100 weight parts and 100 weight part glass powders are dropped in the mixing tank, fully mix, prepare the glass paste of each glass powder.

On the other hand, as glass substrate 42, prepare the soda-lime glass (thermal expansivity 85 * 10 of 120mm square (thick 3mm) ^-7/ ℃, 735 ℃ of softening temperatures, 550 ℃ of second-order transition temperatures).

Use the metal mask of mask thickness 200 μ m on this glass substrate 42, come the coated glass slurry by silk screen print method.In addition, each glass paste is coated glass substrate 42 and is prepared in rear 60 minutes at glass paste and carry out.

Afterwards, the glass substrate 42 that has been coated with glass paste is dropped into drying machine, drying is 40 minutes under 180 ℃, and acquisition is formed with the glass substrate 42 of the pulp layer 50 of thick 200 μ m.

The glass substrate 42 that will be formed with above-mentioned pulp layer 50 is arranged on the press that platform is heated to 200 ℃.

Then, load at pulp layer 50 and to be formed with the concavo-convex plane shaping dies corresponding with round Fresnel lens shown in Figure 5 (nickel system, square, the lens height 100 μ m of size 120mm), glass substrate 42 applied pressures are carried out 60 seconds pressurization as the mode of 35MPa.

Afterwards, with shaping dies 24 demouldings, obtained being formed with mold pressing concavo-convex pulp layer 50 shaping dies 24 shapes, that become optical function section 46.

During the section shape of the pulp layer 50 after observe being shaped with SEM, the lens height of the pulp layer 50 that is formed by arbitrary sample all is 100 μ m, can confirm that the shape of shaping dies 24 is by well transfer printing.

In addition, the volume filling ratio of glass powder is about 60% in the pulp layer 50.

To be formed with mold pressing the glass substrate 42 of pulp layer 50 of shaping dies 24 shapes drop into firing furnaces, the heat-up rate with 5 ℃/minute in air atmosphere is warming up to 450 ℃, 450 ℃ of lower maintenances 90 minutes, carries out the unsticking mixture.

Behind the unsticking mixture, by firing furnace is decompressed to 100Pa, with 5 ℃/minute heat-up rates be warming up to the firing temperature shown in the following table 3, under this temperature the time shown in the maintenance table 3, carry out by this burning till/welding of glass powder.

Afterwards, be cooled to room temperature, obtain the Fresnel lens shown in Figure 5 40 that glass substrate 42 and optical function section 46 directly engage.

About each Fresnel lens 40 and glass paste of making, carry out adaptation, total light transmittance and the mist degree after burning till between slurry life-span (storage stability), glass substrate 42 and the pulp layer 50 of glass paste, the evaluation of the change of shape (shape-holding property) before and after burning till.

In addition, example 8 and sample 1, example 9 and sample 2, example 10 are corresponding respectively with sample 3, and comparative example 5 and sample 9, comparative example 6 and sample 10, comparative example 7 and sample 11, comparative example 8 and sample 12, comparative example 9 and sample 13, comparative example 10 are corresponding with sample 14 difference.

Here, comparative example 7(sample 11) and comparative example 8(sample 12) pulp layer 20 is all peeled off from glass substrate 42 in the pressurization operation, therefore burn till.

In addition, comparative example 9(sample 13) even burn till under the temperature (660 ℃) of glass substrate 42 distortion, glass is not softening yet, can not form optical function section 46, the evaluation after burning till.

[slurry life-span]

Prepare behind the slurry and minute to get a part, with the unvaporized mode encloses container of solvent, at room temperature preserve, estimate the slurry life-span.

Estimate following carrying out.

◎: unchanged more than one month

Zero: one week is above unchanged

△: became glue, and can not be coated with in about one day

*: become glue in several hours, can not be coated with.

[adaptation]

In the aforementioned pressurization operation in the making of Fresnel lens 40, estimate adaptation according to the situation of peeling off of film.

Estimate following carrying out.

◎: have no pulp layer fully and peel off from glass substrate.

Zero: float though see that pulp layer slightly has, be unlikely to peel off, actual use upper no problem.

△: some peels off pulp layer, but overburden amount is less than half.

*: pulp layer has over half peeling off.

[total light transmittance and mist degree]

In aforementioned pressurization operation, except replacing with the smooth SUS plate that does not have a lens shape shaping dies 24 pressurizes, burn till film in the smooth glass system of the surface of glass substrate 42 formation with the making of Fresnel lens 40 identically, make glass board material.Burn till the about 70 μ m of thickness of film.

This glass board material is measured total light transmittance (transmissivity) [%] and mist degree [%] with haze meter (Japanese electric look NDH5000W processed).Total light transmittance more than 85%, better in actual use below 10% of mist degree.

[lens height]

Observe the section of the optical function section 46 after burning till with SEM, measure lens height [μ m].

In addition, as previously mentioned, the filling ratio of glass powder is about 60% in the glass paste bed of material before burning till, so the burn till rear lens limit height of sintering when fully carrying out is about 60 μ m.Better in actual use more than 50 μ m of lens height.

More than the results are shown in following table 4 and table 5.

Table 4

Table 5

As above shown in the table 4, the related use of glass paste of the present invention has example 8～10(sample 1～3 of the glass powder of composition requirement) stability, glass substrate 42 and the pulp layer 50 of glass paste between adaptation and burn till after total light transmittance and the shape stability (lens height) of the optical characteristics such as mist degree and optical function section 46 all good.

The comparative example 5 of the sample 9 that therewith relatively, the use silica content is few can not obtain the shape stability of enough optical function sections 46.In addition, the comparative example 6 of use silicon oxide amount sample 10 still less not only shape stability is not enough, and the optical characteristics such as total light transmittance and mist degree are also not enough.In addition, use the lens coloring of the comparative example 10 of the sample 14 that contains bismuth oxide to become dark brown, be difficult to use as lens.Moreover, want to use the lens height of comparative example 5 of sample 9 more than 50 μ m, then total light transmittance has the tendency that declines to a great extent.

Can clear and definite effect of the present invention from above result.

Utilize possibility on the industry

The present invention can be specially adapted to the manufacturing that the surfaces such as Fresnel lens or lens arra have trickle concavo-convex optics, and the surfaces such as Fresnel lens or microlens array have trickle concavo-convex planar lens.

In addition, quote the full content of Japanese patent application 2010-097938 number of filing an application on April 21st, 2010 and Japanese patent application 2010-097939 number specification sheets, claims, accompanying drawing and the summary of filing an application on April 21st, 2010 here as announcement of the present invention.

Nomenclature

10,40 Fresnel lenses

12,42 glass substrates

14 lens sections

20,50 pulp layers

24 shaping dies

30 roller moulds

34 slurries

46 optical function sections

Claims (14)

1. the manufacture method of glass member made, it is the manufacture method of concavo-convex glass member made that has formed the regulation shape of glass system on the surface of glass substrate, it is characterized in that,

Possesses following operation: use the slurry comprise glass powder, tackiness agent and solvent, form the concavo-convex operation that forms of the described regulation shape that consisted of by described glass powder and tackiness agent on the surface of described glass substrate; Concavo-convexly remove tackiness agent, then make the heating process of glass powder welding with surface from described glass substrate forms,

And the described glass powder of described slurry contains boron oxide and its content below 40 % by mole, and described tackiness agent has hydroxyl.

2. the manufacture method of glass member made as claimed in claim 1 is characterized in that, described formation operation possesses following operation: described slurry is coated the surface of glass substrate and the operation that forms pulp layer, remove described solvent from this pulp layer, and

To have with the shaping dies of the concavo-convex corresponding shape that forms and press on described slurry, the concavo-convex pulp layer that formation has the regulation shape, the operation of then this shaping dies being taken off from pulp layer.

3. the manufacture method of glass member made as claimed in claim 1, it is characterized in that described formation operation possesses to be coated described slurry concavo-convex roller mould with regulation shape, formed the operation of the concavo-convex pulp layer with regulation shape by this roller mould at described glass baseplate surface.

4. the manufacture method of glass member made as claimed in claim 2 is characterized in that, before pressing described shaping dies, the pulp layer of having removed described solvent is heated to the softening temperature of described tackiness agent.

5. such as the manufacture method of each described glass member made in the claim 1～4, it is characterized in that described tackiness agent is butyral resin.

6. such as the manufacture method of each described glass member made in the claim 1～5, it is characterized in that the content of the boron oxide that described glass powder is contained is more than 3 % by mole, below 40 % by mole.

7. planar lens is characterized in that, forms by forming the optical function section that different glass consists of from described glass substrate at glass substrate, and the glass that consists of this optical function section is the glass that comprises following composition with % by mole expression of oxide compound benchmark:

Silicon oxide 40～64%,

Boron oxide 5～35%,

Zinc oxide 2～30%,

Aluminum oxide 1～10%,

At least a of Lithium Oxide 98min, sodium oxide and potassium oxide adds up to 10～22%,

At least a of barium oxide and strontium oxide adds up to 0～10%.

8. planar lens as claimed in claim 7 is characterized in that, except as the occasion that contains from the impurity of other compositions, the glass that consists of described optical function section is not bismuth-containing compound, lead compound and phosphorus compound in fact.

9. such as claim 7 or 8 described planar lenss, it is characterized in that described glass substrate is 75 * 10 at 50～350 ℃ average coefficient of linear expansion ^-7～100 * 10 ^-7/ ℃.

10. such as each described planar lens in the claim 7～9, it is characterized in that the second-order transition temperature of described glass substrate is 550～670 ℃.

11. glass paste, it is characterized in that, comprise glass powder, tackiness agent and solvent, wherein said glass powder comprises following composition with % by mole expression of oxide compound benchmark: silicon oxide 40～64%, boron oxide 5～35%, zinc oxide 2～30%, aluminum oxide 1～10%, the at least a of Lithium Oxide 98min, sodium oxide and potassium oxide adds up to 10～22%, at least a 0～10% of barium oxide and strontium oxide.

12. glass paste as claimed in claim 11 is characterized in that, except as the occasion that contains from the impurity of other compositions, described glass is not bismuth-containing compound, lead compound and phosphorus compound in fact.

13., it is characterized in that described tackiness agent is the resin with hydroxyl such as claim 11 or 12 described glass pastes.

14. glass paste as claimed in claim 13 is characterized in that, described tackiness agent is butyral resin.

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