CN100575396C - Aliphatic polyester-based resin reflective film and reflector - Google Patents
Aliphatic polyester-based resin reflective film and reflector Download PDFInfo
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- CN100575396C CN100575396C CN200580024105A CN200580024105A CN100575396C CN 100575396 C CN100575396 C CN 100575396C CN 200580024105 A CN200580024105 A CN 200580024105A CN 200580024105 A CN200580024105 A CN 200580024105A CN 100575396 C CN100575396 C CN 100575396C
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Abstract
The invention provides and a kind ofly have excellent light reflective, and can not pass in time in use and produce the aliphatic polyester-based resin reflective film of yellowing.This aliphatic polyester-based resin reflective film is formed by resin combination, and described resin combination contains aliphatic polyester-based resin and based on the microgranular weighting agent of titanium oxide, wherein, the content of niobium in this titanium oxide is below the 500ppm.In addition, this titania surface preferably is selected from least a nonactive inorganic oxide coating in silicon-dioxide, aluminum oxide and the zirconium white.
Description
Technical field
The present invention relates to aliphatic polyester-based resin reflective film, particularly, relate to the reflectance coating that in liquid crystal indicator, the reflectors such as instrument, lighting advertisement board that throw light on etc., uses.In addition, relate to the reflector that above-mentioned reflectance coating is coated on the use in liquid crystal indicator, illumination instrument, lighting advertisement board etc. that metal sheet, resin board etc. are gone up and form.
Background technology
In recent years, being used for the reflector of liquid crystal indicator, projection, use reflectance coating with the parts of projection screen or flat light source, be used to the throw light on reflector of instrument and the fields such as reflector that are used for the lighting advertisement board.For example, in the reflector of liquid-crystal display, from the big pictureization of device and the requirement of the High Level of display performance, though for more as far as possible less light is supplied to the performance that improves backlight unit in the liquid crystal, require highly reflective can reflectance coating.
As reflectance coating, known have the white tablets (for example, with reference to patent documentation 1) of adding titanium oxide and forming in aromatic polyester-based resin, but be not the reflectance coating with high light reflective of requirement.In addition, also have by being stretching in the sheet that absorb fillers forms in the aromatic polyester-based resin, in sheet, form fine space, thereby the reflectance coating of generation scattering of light reflection (for example, with reference to patent documentation 2), but be not the reflectance coating with high light reflective of requirement.In addition, because the aromatic nucleus that contains in the molecular chain of the aromatic polyester-based resin that forms them absorbs ultraviolet ray, therefore exist the ultraviolet ray of sending to cause film deterioration, yellowing, thereby make the shortcomings such as light reflective reduction of reflectance coating owing to light source from liquid crystal indicator etc.
In addition, in recent years, there is the reflectance coating that to have implemented warpage processing etc. to be encased in the example that uses in the liquid crystal indicator.At this moment, the shape-holding property of the shape when reflectance coating is required to keep warpage, but there is the insufficient shortcoming of shape-holding property in reflectance coating in the past.
Patent documentation 1: the spy opens the 2002-138150 communique
Patent documentation 2: the spy opens flat 4-239540 communique
Summary of the invention
The problem that invention will solve
The present invention makes in order to address the above problem, and the object of the present invention is to provide a kind of reflectance coating, and this reflectance coating has excellent light reflective, and can not pass in time in use and produce yellowing.
Solve the method for problem
Reflectance coating of the present invention is formed by resin combination, and described resin combination contains aliphatic polyester-based resin and based on the microgranular weighting agent of titanium oxide, wherein, the content of niobium in this titanium oxide is below the 500ppm.
In addition, titania surface preferably is selected from least a nonactive inorganic oxide coating in silicon-dioxide, aluminum oxide and the zirconium white.
Wherein, the preferred 3 quality % of the surface treatment amount～9 quality % of the titanium oxide that coats by above-mentioned nonactive inorganic oxide.
In addition, in the aliphatic polyester resin composition that contains fine powdered weighting agent and aliphatic polyester-based resin, the preferred 10 quality % of the content of fine powdered weighting agent～60 quality %.
In addition, the specific refractory power of aliphatic polyester-based resin preferably is lower than 1.52, and special preferred aliphat polyester resin is a lactide acid polymer.
In addition, preferably have the space, and to make voidage be below 50% in inside.
In addition, preferably fusion system film is contained the aliphatic polyester resin composition of aliphatic polyester-based resin and fine powdered weighting agent and the film that obtains at least at stretch film more than 1.1 times of single shaft direction.
Reflector of the present invention is characterised in that to have above-mentioned aliphatic polyester-based resin reflective film.
The effect of invention
According to the present invention, can obtain having high light reflective, and can not pass in time and produce the reflectance coating of yellowing.In addition, by on metal sheet or resin board, coating reflectance coating of the present invention, can obtain having the reflector that in liquid crystal indicator, illumination instrument, lighting advertisement board etc., uses of high light reflective.
Embodiment
Below, explain the present invention.In addition, the situation that in the present invention, is called " film " also comprises " sheet ", and the situation that is called " sheet " also comprises " film ".
Aliphatic polyester-based resin reflective film of the present invention has the fine powdered weighting agent based on titanium oxide in inside.Because the specific refractory power height of titanium oxide, can strengthen the refringence with base resin, therefore, can give high reflecting properties to film with loading level still less, in addition, even can obtain thin-walled also have highly reflective can film.
As the titanium oxide that uses among the present invention, can enumerate, for example, the titanium oxide of the crystalline form that anatase titanium dioxide and rutile-type are such.From the viewpoint of increasing with the refringence of base resin, preferred index is the titanium oxide more than 2.7, for example, preferably uses the titanium oxide of rutile-type crystalline form.
Wherein, for film being given high light reflective, must use the little titanium oxide of photoabsorption energy to visible light.In order to reduce the photoabsorption energy of titanium oxide, preferably reduce the amount of the coloring element that contains in this titanium oxide, particularly, be below the 500ppm by the content that makes niobium, can obtain having the reflectance coating of high light reflective.
As the titanium oxide that uses among the present invention, can enumerate titanium oxide made from chlorine method technology and the titanium oxide made from sulfuric acid process.Wherein, owing to the purity of the titanium oxide made from chlorine method technology is higher, for example, the content of the niobium that contains in this titanium oxide reaches below the 500ppm easily, therefore is applicable to this reflectance coating.
In chlorine method technology, at first make with the titanium oxide be in the rutile ore of main component or the High Temperature Furnaces Heating Apparatus of titania about 1000 ℃ with chlorine reaction, generate titanium tetrachloride.Then, by this titanium tetrachloride of burning in oxygen, can obtain content of niobium is the following titanium oxide of 500ppm.
In addition, the titanium oxide that uses among the present invention preferably coats processing with at least a nonactive inorganic oxide that is selected from silicon-dioxide, aluminum oxide and the zirconium white to the surface of this titanium oxide.In order to improve the photostabilization of film,, preferably the surface of this titanium oxide is coated processing with nonactive inorganic oxide perhaps for the photocatalytic activity of inhibited oxidation titanium.When use is selected from this nonactive inorganic oxide of at least a conduct in silicon-dioxide, aluminum oxide and the zirconium white, owing to can not damage the high light reflectivity of titanium oxide, so preferably.In addition, be more preferably and use these nonactive inorganic oxides more than 2 kinds simultaneously, wherein, preferred especially is the combination of the multiple nonactive inorganic oxide of necessary selection component with silicon-dioxide.
In the present invention, when surface treatment is carried out on the surface of titanium oxide, adopt the preferred 3 quality % of the surface treatment amount～9 quality % of the titanium oxide that nonactive inorganic oxide carries out with nonactive inorganic oxide.If this surface treatment amount is more than the 3 quality %, keep high light reflective easily, in addition,,, can obtain the film of homogeneous to the favorable dispersity of aliphatic polyester-based resin if be below the 9 quality %.Here said " surface treatment amount ", be quality with the nonactive inorganic oxide that coats titania surface divided by nonactive inorganic oxide, the total mass that is used to improve dispersed following mineral compound and carries out various surface-treated titanium oxide with organic compound etc., be the numerical value of representing with %, and represent with mean value.
In addition, in order to improve the dispersiveness of titanium oxide, can also carry out surface treatment to the surface of titanium oxide with at least a organic compound that is selected from least a mineral compound in silicone compounds, the silane coupling agent etc. or be selected from polyvalent alcohol, the polyoxyethylene glycol etc. to resin.
The titanium oxide preferable particle size of using among the present invention is 0.1 μ m～1 μ m, is more preferably 0.2 μ m～0.5 μ m.If the particle diameter of titanium oxide is more than the 0.1 μ m,, can obtain the film of homogeneous to the favorable dispersity of aliphatic polyester-based resin.In addition, if the particle diameter of titanium oxide is below the 1 μ m,, therefore can give high light reflective to reflectance coating owing to form the interface of aliphatic polyester-based resin and titanium oxide densely.
In the present invention, as other the fine powdered weighting agent that can use with titanium oxide, can enumerate organic fines, inorganic fines etc.
As organic fines, preferred use at least a in cellulose-type powders such as being selected from wood powder, paper pulp powder and polymeric beads, the polymkeric substance hollow-particle etc.
As inorganic fines, the preferred use is selected from least a in lime carbonate, magnesiumcarbonate, barium carbonate, sal epsom, barium sulfate, calcium sulfate, zinc oxide, magnesium oxide, calcium oxide, aluminum oxide, aluminium hydroxide, hydroxyapatite, silicon-dioxide, mica, talcum, potter's clay, clay, glass powder, asbestos powder, zeolite, the silicic acid carclazyte etc.If the light reflective of the film that consideration obtains, preferably big material with the refringence of the film forming base resin of structure, that is, as inorganic fines, the material that preferred index is big.Particularly, be more preferably that to use specific refractory power be lime carbonate, barium sulfate or zinc oxide more than 1.6.
In addition, for the fine powdered weighting agent beyond the titanium oxide, in order to improve dispersiveness, can use with silicon compounds, multicomponent alcoholics compound, aminated compounds, lipid acid, fatty acid ester etc. the surface-treated weighting agent has been implemented on the surface of fine powdered weighting agent resin.
As the fine powdered weighting agent beyond the titanium oxide that can use in the present invention, preferable particle size is 0.05 μ m～15 μ m, and being more preferably particle diameter is 0.1 μ m～10 μ m.If the particle diameter of fine powdered weighting agent is more than the 0.05 μ m,, therefore can obtain the film of homogeneous owing to can not reduce to the dispersiveness of aliphatic polyester-based resin.In addition, if particle diameter is below the 15 μ m, the space of formation can chap, can obtain the film of high-reflectivity.
Fine powdered weighting agent based on titanium oxide preferably disperses to be added in the aliphatic polyester-based resin.When considering the light reflective, mechanical properties, productivity etc. of film, in being used to form the aliphatic polyester resin composition of reflectance coating, the content of the fine powdered weighting agent that contains in the reflectance coating of the present invention is preferably 10 quality %～60 quality %, be more preferably 10 quality %～55 quality %, preferred especially 20 quality %～50 quality %.If the content of fine powdered weighting agent is more than the 10 quality %, can fully guarantees the area at the interface of resin and fine powdered weighting agent, thereby can give high light reflective film.In addition, if the content of fine powdered weighting agent is below the 60 quality %, can guarantee the necessary mechanical properties of film.
From this point of reflectivity, aliphatic polyester-based resin reflective film of the present invention preferably has the space in inside, and voidage (space in film shared ratio) is below 50%.In the present invention, by containing the fine powdered weighting agent effectively with dispersion state, can realize excellent more reflectivity in film inside.
When aliphatic polyester-based resin reflective film of the present invention had the space in film, preferably this space shared ratio (voidage) in film was in 5%～50% the scope.In addition, from improving this point of reflectivity, voidage is more preferably more than 20%, and is preferred especially more than 30%.Voidage surpasses at 50% o'clock, and the physical strength of film reduces sometimes, film fracture in the manufacturing of film, perhaps weather resistance deficiency such as thermotolerance in use.For example, by adding the fine powdered weighting agent and stretching, can in film, form the space.
In the present invention, as the fine powdered weighting agent, owing to mainly use content of niobium to be the titanium oxide below the 500ppm, therefore, even under the few situation of the inner voidage that exists of film, also can realize high light reflective, even and do not have the space in inside, also can obtain high-reflectivity.Infer that this is owing to bring into play the specific refractory power height of titanium oxide, the feature that the power of covering is high effectively.In addition,,, therefore, can keep high reflecting properties, improve the mechanical properties of film simultaneously because the quantity in the space that forms by stretching also tails off if can reduce the usage quantity of weighting agent.In addition,, reduce the space, mechanical properties is improved by reducing amount of tension even the usage quantity of weighting agent is many.These also are favourable on this aspect of dimensional stability that improves film.In addition, if, then can be used as the uses such as reflectance coating that for example are used for small-sized, slim liquid-crystal display such as subnotebook PC or mobile phone even when thin-walled, also can guarantee high reflecting properties.
The base resin preferred index (n) that constitutes reflectance coating of the present invention is lower than 1.52, in the present invention, preferably uses specific refractory power (n) to be lower than 1.52 aliphatic polyester-based resin.
In addition, specific refractory power (n) is lower than 1.52 resin and is more preferably as the resinoid polylactic acid base polymer of aliphatics that does not contain aromatic nucleus.The material that contains aromatic nucleus, for example the specific refractory power of aromatic resin is about more than 1.55.
The reflectance coating that contains fine powdered weighting agents such as titanium oxide at film utilizes the refraction scattering at the interface of film forming resin of structure and fine powdered weighting agent to show light reflective.This refraction reflecting effect is along with the change of the refringence of resin and fine powdered weighting agent becomes big greatly.Therefore, as the resin that uses among the present invention, preferably with the fine powdered weighting agent littler resin of specific refractivity mutually, particularly, preferred index is lower than 1.52 aliphatic polyester-based resin, is more preferably specific refractory power and is lower than 1.46 lactide acid polymer.
Aliphatic polyester-based resin is not owing to containing aromatic nucleus, so can not cause ultraviolet radiation absorption in molecular chain.Therefore, the ultraviolet ray that can send owing to the light source from liquid crystal indicator etc. does not cause film deterioration, yellowing, and light reflective can not reduce.
As aliphatic polyester-based resin, can use the polyester resin of chemosynthesis, by microbial fermentation synthetic polyester resin and their mixture.Aliphatic polyester-based resin as chemosynthesis, can enumerate the polyethylene glycol adipate that lactone ring opening polymerization obtained poly-epsilon-caprolactone etc., diprotic acid and dibasic alcohol polymerization and obtain, polyethylene glycol azeleate, polytetramethylene succinate, cyclohexane cyclohexanedimethanodibasic/cyclohexanedimethanol condenses etc., the poly(lactic acid) that the hydroxycarboxylic acid polymerization is obtained, polyoxyethylene glycol etc., with the part of the ester bond of above-mentioned aliphatic polyester, for example replace to the aliphatic polyester of amido linkage, ehter bond, amino-formate bond etc. below 50%.In addition, as by microbial fermentation synthetic aliphatic polyester-based resin, can enumerate the multipolymer of polyhydroxybutyrate (polyhydroxybutyrate), hydroxybutyric acid (hydroxybutyrate) and hydroxypentanoic acid (hydroxyvalerate) etc.
In the present invention, so-called lactide acid polymer, be meant the homopolymer of D-lactic acid or L-lactic acid or their multipolymer, particularly, it is that poly-(D-lactic acid), the structural unit of D-lactic acid is poly-(the L-lactic acid) of L-lactic acid and as poly-(the DL-lactic acid) of the multipolymer of L-lactic acid and D-lactic acid that structural unit is arranged, in addition, the mixture that also comprises them.
Owing in molecular chain, do not contain aromatic nucleus, therefore do not cause ultraviolet radiation absorption with the aliphatic polyester-based resin headed by the lactide acid polymer.Therefore, down reflectance coating can deterioration or yellowing to be exposed to ultraviolet ray, and therefore, the reflectivity of film can not reduce.
Lactide acid polymer can be by known method manufacturings such as polycondensation method, ring-opening polymerization methods.For example, in the polycondensation method, can obtain having the lactide acid polymer of any composition directly with D-lactic acid, L-lactic acid or their mixture dehydration polycondensation.In addition, in the ring-opening polymerization method, can use polymerization regulator etc. as required, and in the presence of the catalyzer of regulation, will carry out ring-opening polymerization, obtain having the lactide acid polymer of any composition as the lactide of the cyclic dimer of lactic acid.In above-mentioned lactide, L-lactide as the L-lactic acid dimer is arranged, as the D-lactide of D-lactic acid dimer, as the DL-lactide of D-lactic acid and L-lactic acid dimer, can as required they be mixed and carry out polymerization, obtain having any composition, crystalline lactide acid polymer.
The D-lactic acid of the lactide acid polymer that uses among the present invention and the constituent ratio of L-lactic acid are preferably D-lactic acid: L-lactic acid=100: 0～85: 15, perhaps D-lactic acid: L-lactic acid=0: 100～15: 85, be more preferably D-lactic acid: L-lactic acid=99.5: 0.5～95: 5, perhaps D-lactic acid: L-lactic acid=0.5: 99.5～5: 95.The constituent ratio of D-lactic acid and L-lactic acid is that the lactide acid polymer of 100: 0 or 0: 100 shows very high crystallinity, and has the tendency of fusing point height, thermotolerance and mechanical properties excellence.That is, film is stretched or during thermal treatment, resin generation crystallization, thermotolerance and mechanical properties improve, so preferably.On the other hand, the lactide acid polymer that is made of D-lactic acid and L-lactic acid be owing to can give flexibility, and improves the forming stability of film and the stability that stretches, so preferably.Therefore, when the balance of the thermotolerance and the forming stability of the reflectance coating of considering to obtain and the stability that stretches, the D-lactic acid of the lactide acid polymer that the present invention uses and the constituent ratio of L-lactic acid are more preferably D-lactic acid: L-lactic acid=99.5: 0.5～95: 5, or D-lactic acid: L-lactic acid=0.5: 99.5～5: 95.
In the present invention, also can the blending D-lactic acid lactide acid polymer different with the copolymerization ratio of L-lactic acid.At this moment, as long as the mean value of the copolymerization ratio of the D-lactic acid of multiple lactide acid polymer and L-lactic acid falls in the above-mentioned scope.By the homopolymer and the multipolymer of blending D-lactic acid and L-lactic acid, can obtain to be difficult for oozing out the balance of (bleed) property and stable on heating performance.
The preferred high-molecular weight of the lactide acid polymer that uses among the present invention, for example, preferable weight-average molecular weight is more than 50,000, is more preferably 60,000～400,000, preferred especially 100,000～300,000.The weight-average molecular weight of lactide acid polymer is lower than at 50,000 o'clock, and the mechanical properties of the film that obtains sometimes is poor.
In recent years, liquid-crystal display except that use PC with indicating meter on, also use at onboard navigation system that is used for automobile or vehicle mounted minitelevision etc., therefore need withstand high temperatures degree, high humidity.Therefore, in order to give weather resistance, preferably add hydrolysis and prevent agent aliphatic polyester-based resin reflective film.
Prevent agent as the preferred hydrolysis of using among the present invention, can enumerate carbodiimide compound etc.As carbodiimide compound, for example, the carbodiimide compound that can enumerate the basic structure with following general formula is as preferred material.
-(N＝C＝N-R-)
n-
In the formula, n represents the integer more than 1, and R represents organic class combining unit.For example, R can be aliphatics, alicyclic, aromatic any.In addition, n selects suitable integer usually between 1～50.
Particularly, as carbodiimide compound, can enumerate, for example, two (dipropyl phenyl) carbodiimide, poly-(4,4 '-ditane carbodiimide), poly-(to the phenylene carbodiimide), poly-(metaphenylene carbodiimide), poly-(tolyl carbodiimide), poly-(di-isopropyl phenylene carbodiimide), poly-(methyl di-isopropyl phenylene carbodiimide), poly-(triisopropyl phenylene carbodiimide) etc. and their monomer.These carbodiimide compounds can be used singly or in combination of two or more thereof.
In the present invention, with respect to the film forming aliphatic polyester-based resin of 100 mass parts structures, preferably add 0.1～3.0 mass parts carbodiimide compound.If the addition of carbodiimide compound is more than 0.1 mass parts, in the film that obtains, can show the effect of improving of hydrolytic resistance fully.In addition, if the addition of carbodiimide compound is below 3.0 mass parts, the film that obtains painted few can obtain high light reflective.
In the present invention, in the scope of not damaging effect of the present invention, can add oxidation inhibitor, photostabilizer, thermo-stabilizer, lubricant, dispersion agent, UV light absorber, white pigment, white dyes and other additive.
In addition, aliphatic polyester-based resin reflective film preferred surface of the present invention is more than 95%, to be more preferably more than 97% to the reflection of light rate of the about 550nm of wavelength.If this reflectivity is more than 95%, then show good reflection characteristic, can give sufficient lightness to the picture of liquid-crystal display etc.
In addition, even also can keep excellent reflectivity after aliphatic polyester-based resin reflective film of the present invention tans by the sun under ultraviolet ray.
, under the weather of sweltering heat in summer, in the car in parking lot, automobile carries navigationsystem, vehicle mounted minitelevision etc. and is exposed in the high temperature.In addition, when long-time use liquid crystal indicator, also be exposed in the high temperature around the illuminator.Therefore, require thermotolerance about 110 ℃ for the reflectance coating that uses in the liquid-crystal displays such as onboard navigation system, liquid crystal indicator.That is, the percent thermal shrinkage of the film when reflectance coating is placed 5 minutes under 120 ℃ temperature is preferably below 10%, is more preferably below 5%.When the percent thermal shrinkage of film is bigger than 10%, when at high temperature using, cause contraction sometimes with the passing of time, reflectance coating is stacked in steel plate etc. when going up, and only causes the film distortion sometimes.Produce the film of big contraction owing to promote the surface of reflection to diminish, perhaps the space of film inside diminishes, so reflectivity reduces.
In order to prevent thermal contraction, wish the crystallization of film is carried out fully.Aliphatic polyester-based resin reflective film is owing to only be difficult to therefore, in the present invention, preferably to carry out the heat setting type processing after stretching by biaxial stretch-formed and fully carry out crystallization.By promoting the crystallization of film, can give thermotolerance to film, hydrolytic resistance is improved.
Aliphatic polyester-based resin reflective film of the present invention can not produce the problem on discarding by decomposition such as microorganisms when landfill disposal.During the landfill disposal aliphatic polyester-based resin, molecular weight is reduced to about 1000, then by the biological degradations such as microorganism in the soil by hydrolyse ester bond.
On the other hand, the intramolecular combination stability height of aromatic polyester-based resin is difficult to cause the hydrolysis of ester bond part.Therefore, even aromatic polyester-based resin is carried out landfill disposal, molecular weight does not reduce yet, and can not cause the biological degradation of being undertaken by microorganism etc. yet.Its result, the normal phase remains in the soil, produces the short lifeization that promotes waste landfill disposal land used, perhaps impairs the problems such as living environment of natural landscape or wild fauna and flora.
Below, giving an example illustrates the manufacture method of aliphatic polyester-based resin reflective film of the present invention, but the present invention is not subjected to any qualification of following manufacturing process.
At first, fine powdered weighting agent, the hydrolysis based on titanium oxide of adding content of niobium as required be in aliphatic polyester-based resin below the 500ppm prevents agent, other additives etc., the making aliphatic polyester resin composition.
Particularly, fine powdered weighting agent, the hydrolysis based on the titanium oxide that add content of niobium as required be in aliphatic polyester-based resin below the 500ppm prevent agent etc., after mixing such as ribbon blender, tumbler mixer, Henschel mixing tank, (for example use the temperature more than the fusing point of resin such as Banbury mixing tank, single shaft or biaxial extruder, be 170 ℃～230 ℃ under the situation of poly(lactic acid)) carry out mixingly, can obtain aliphatic polyester resin composition.In addition, the content of niobium that can add specified amount by each feeding unit be that fine powdered weighting agent, hydrolysis based on titanium oxide below the 500ppm prevents that agent from waiting and obtain aliphatic polyester resin composition.Perhaps, fine powdered weighting agent, the hydrolysis based on titanium oxide adding content of niobium in advance on aliphatic polyester-based resin middle and high concentration ground and be below the 500ppm prevent agent etc., make so-called main sizing material, should mix with aliphatic polyester-based resin by main sizing material, can make the aliphatic polyester resin composition of expectation concentration.
Then, with the aliphatic polyester resin composition fusion that obtains like this, form membranaceous.For example, after aliphatic polyester-based resin constituent drying, supply in the forcing machine, the above temperature of fusing point that is heated to resin is carried out fusion.Perhaps, also can moist aliphatic polyester resin composition and directly supply in the forcing machine, still, under moist situation, preferably when melt extruding, use vacuum outlet.
Conditions such as extrusion temperature must consider that the situation that molecular weight is reduced waits and set, for example, if under the situation of poly(lactic acid), the scope that extrusion temperature is preferred 170 ℃～230 ℃.Then, the fused aliphatic polyester resin composition is extruded from the slit-shaped discharge opening of T pattern, made its adhering and solidifying on cooling roller, form cast sheet.
Reflectance coating of the present invention can obtain by the following method: with adding aliphatic polyester-based resin and content of niobium is the resin combination fusion system film that the fine powdered weighting agent based on titanium oxide below the 500ppm forms, and stretches more than 1.1 times in the single shaft direction at least then.By stretched film, be the space of nuclear inner formation of film, and then the light reflective of film is improved, so preferred with the titanium oxide.Can think that this is because form the interface in resin and space and the interface of space and titanium oxide again, thereby the effect of the refraction scattering that produces at the interface increases.
In addition, reflectance coating of the present invention preferably is drawn into more than 5 times with the area dynameter, is more preferably to be drawn into more than 7 times.By on the area multiplying power film being drawn into more than 5 times, can be in the inner voidage that realizes more than 5% of reflectance coating, by film being drawn into more than 7 times, can be in the inner voidage that realizes more than 20% of reflectance coating, by film being drawn into more than 7.5 times, can also be in the inner voidage that realizes more than 30% of reflectance coating.
Reflectance coating of the present invention is more preferably at biaxially oriented and stretches.This be because, biaxial stretch-formed by film is carried out, can stablize and obtain to have the more film of high voidage, thereby improve the light reflective of film.
When film was carried out uniaxial extension, the space of formation was the fibrous form in the elongation of direction, carried out when biaxial stretch-formed, and the space becomes in the discoid form of both direction elongation in length and breadth.That is, biaxial stretch-formed by carrying out, the area of peeling off at the interface of resin and titanium oxide increases, and carries out the albefaction of film, and its result can improve the light reflective of film.
In addition, when reflectance coating is required thermotolerance, film is carried out owing to disappear in the shrinkage direction anisotropy of film, therefore preferably carrying out film biaxial stretch-formed when biaxial stretch-formed.In addition, biaxial stretch-formed by film is carried out, the physical strength of film is increased.
Draft temperature during the stretching casting films preferably constitutes the interior temperature of the scope that second-order transition temperature (Tg) degree is above, (Tg+50 ℃) degree is following of the base resin of sheet, for example, when base resin is poly(lactic acid), preferred 50 ℃～90 ℃ of draft temperature.If draft temperature is this scope, film can not rupture when stretching, and stretch orientation is uprised, and can strengthen voidage, therefore can obtain having the film of high-reflectivity.
For example, wait drawing fat adoption esters resin film by suitable selection stretching ratio, in the inner space that forms of film, this is because aliphatic polyester-based resin is different with the stretch behavior of fine powdered weighting agent when stretching.Promptly, if stretch under the draft temperature of aliphatic polyester-based resin being suitable for, though the aliphatic polyester-based resin as matrix is stretched, but because the fine powdered weighting agent will stop with the state of keeping intact, so the interface peel of aliphatic polyester-based resin and fine powdered weighting agent, thereby form the space.When only film being carried out uniaxial extension, the space of formation only becomes the fibrous form in the elongation of direction, but biaxial stretch-formed by carrying out, and this space becomes in the space of both direction elongation in length and breadth, becomes discoid form.In other words, biaxial stretch-formed by carrying out, the area of peeling off at the interface of aliphatic polyester-based resin and fine powdered weighting agent increases, and carries out the albefaction of film, and its result as reflectance coating, obtains good reflectivity.
Biaxial stretch-formed stretching has no particular limits in proper order, for example, can carry out biaxial stretch-formedly simultaneously, also can stretch successively.Behind the use stretcher fusion system film, after can stretching along MD by the roller stretching, stretching by tenter machine stretches along TD again, can also be undertaken biaxial stretch-formed by tubular type (チ ユ one Block ラ one) stretching etc.
In the present invention, for aliphatic polyester-based resin reflective film being given thermotolerance and dimensional stability, preferably after stretching, carry out heat setting type.
Be used for film is carried out preferred 90～160 ℃ of the treatment temp of heat setting type, be more preferably 110～140 ℃.Preferred 1 second～5 minutes of desired treatment time of heat setting type.In addition, be not particularly limited, stretch but preferably after stretching, carry out to carry out the tenter machine that heat setting type handles for stretcher etc.
The thickness of aliphatic polyester-based resin reflective film of the present invention is not particularly limited, and is generally 30 μ m～500 μ m, when considering the operability aspect practical, is preferably in the scope about 50 μ m～500 μ m.Particularly, as the reflectance coating of small-sized, slim reflector purposes, preferred thickness is 30 μ m～100 μ m.If use the reflectance coating of such thickness, can also use in small-sized, slim liquid-crystal display such as for example subnotebook PC or mobile phone etc. etc.
In addition, reflectance coating of the present invention can be a single layer structure, also can be the multilayered structure of lamination more than 2 layers.
In addition, use aliphatic polyester-based resin reflective film of the present invention can be formed on the middle reflectors that use such as liquid-crystal display.For example, aliphatic polyester-based resin reflective film can be coated on metal sheet or the resin board and form reflector.This reflector is useful as the reflector that uses in liquid crystal indicator, illumination instrument, the lighting advertisement plate etc.Below, the manufacture method of the such reflector of explanation of giving an example.
As the method that reflectance coating is coated on metal sheet or the resin board, the method for using caking agent is arranged, do not use caking agent and carry out the method for heat fusion, carry out bonding method, extrusion coated method etc. by the cementability sheet, but not special the qualification.For example, can be on the face of a side of the reflectance coating of applying metal sheet or resin board, caking agents such as coated polyester class, polyurethanes, epoxies, the reflectance coating of fitting again.In the method, use contrary roll-coater, lick and be coated with roll-coater normally used coating apparatus such as (kiss roll coater), at the surface coated caking agent of metal sheet of applying reflectance coating etc., and its dried adhesive film thickness is reached about 2～4 μ m.Then, carry out the dry of coated face and heating, the surface of plate is remained on the temperature of regulation, directly use roll laminating machine (roll laminator) to coat, cool off reflectance coating simultaneously, can obtain reflector thus by infrared heater and hot-blast heater.At this moment, when remaining on the surface of metal sheet etc. below 210 ℃, the light reflective of reflector can be maintained high level, so preferred.
Embodiment
Embodiment below is shown, more specifically describes the present invention, but the present invention is not limited to these, in the scope that does not break away from technological thought of the present invention, can carry out various application.In addition, measured value shown in the embodiment and evaluation are carried out according to as follows.Here, be MD with traction (transmission) direction indication of film, its vertical direction is expressed as TD.
(measuring and evaluation method)
(1) specific refractory power
The specific refractory power of resin is measured based on the A method of JIS K-7142.
(2) content of niobium in the titanium oxide (ppm)
Measure content of niobium based on JIS M-8321 " titanium ore-niobium quantivative approach ".Promptly, take by weighing the 0.5g sample, this sample is moved in the nickel system crucible that has added 5g fusing auxiliary agent (fusion aid) [sodium hydroxide: sodium peroxide=1: 2 (mass ratio)], after the stirring, coat the surface of this test portion with the anhydrous sodium carbonate of about 2g, in crucible,, form melts with the test portion heating and melting.With after being placed in the state naturally cooling in the crucible, a small amount of respectively 100ml warm water and 50ml hydrochloric acid of adding makes it dissolving in melts, adds entry again with this melts, and making capacity is (メ ス ア Star プ) 250ml.Measure this solution with the luminous light-dividing device of ICP, obtain content of niobium.Wherein, measuring wavelength is 309.42nm.
(3) median size
The model of using (strain) Shimadzu Seisakusho Ltd. to make is the long-pending tester (penetrant method) of the specific surface area of " SS-100 ", is 2cm at sectional area
2, highly be to fill the 3g sample in the test specimen tube of 1cm, and calculate by the time that in the 500mm water column, sees through the air of 20cc.
(4) voidage (%)
Measure the density (being labeled as " unstretching film density ") of the film before stretching and the density (being labeled as " stretched film density ") of the film after the stretching, be updated in the following formula, obtain the voidage of film.
Voidage (%)={ (unstretching film density-stretched film density)/unstretching film density } * 100
(5) reflectivity (%)
In spectrophotometer (" U-4000 ", (strain) Hitachi makes), integrating sphere is installed, is measured reflection of light rate for wavelength 550nm.In addition, before the mensuration, be that spectrophotometer is set on 100% ground according to the reflectivity of aluminum oxide blank.
(6) hydrolytic resistance
Film placed 1000 hours in the constant temperature and humidity cabinet that remains 60 ℃ of temperature, relative humidity 95%RH after, measure the weight-average molecular weight of the film forming aliphatic polyester-based resin of structure.Measured value is updated in the following formula, obtains molecular weight conservation rate (%), and carry out the evaluation of hydrolytic resistance according to following metewand.Wherein, mark " zero " and " △ " are more than the realistic scale.
Molecular weight conservation rate (%)=(placing the preceding weight-average molecular weight of back weight-average molecular weight/placement) * 100
Metewand:
Zero molecular weight conservation rate is the situation more than 90%
△ molecular weight conservation rate is more than 60% but is lower than 90% situation
* molecular weight conservation rate is lower than 60% situation
(7) preventing property of yellowing
In sunlight burn-in test tester (intermittent spraying that does not have water), to film irradiation ultraviolet ray in 1000 hours.Then, the surface of the film that detects by an unaided eye is by visual determination, with the tone on film surface be expressed as " in vain " for white, be expressed as " Huang " that turns to be yellow.
In addition, the film after the uviolizing is also measured reflectivity (%) according to the measuring method of above-mentioned (5).
(8) shape-holding property
Estimate by folding (デ Star De Off オ one Le De) the property test of following inefficacy.
That is, at first with the long dimensional directions of film as width, with perpendicular direction as length direction, cut out the sample film of width 20mm, length 150mm.A short brink that keeps this sample film, another minor face (the other end) lateral buckling 180 degree that will not keep in position from the other end 30mm, and the straight line that makes this position becomes the folding line (or recessed folding line (folding リ paddy)) of projection, applies the load of 0.15MPa.The load that applies 0.15MPa is removed load after 0.5 second immediately, opens the part of bending, with hand the other end is turned back to original position, then, hand is left, and measures the angle that keeps owing to bending.That is, when hand is left, measure the angle of the other end from original position deviation with protractor.This numerical value is 180 degree to the maximum, and minimum is 0 degree, and this numerical value is big more, and the inefficacy folding property is excellent more, that is, shape-holding property is excellent more.
(9) reflector processibility
Based on following metewand, to right-angle bending (R=0mm), screw rod driving fit bending, well type cupping (リ Network セ Application) 5mm) 3 projects estimate.
Metewand:
Zero does not have peeling off of film
* peeling off of film arranged
(10) baffle reflection rate
According to the measuring method of above-mentioned (5), measure the reflectivity (%) of reflector.
[embodiment 1]
Lactide acid polymer (NW4032D: カ one ギ Le ダ ウ Port リ マ one company manufacturing with weight-average molecular weight 200,000, D body burden 1.5%) particle and median size are that the titanium oxide ( イ ペ one Network PF-740: the former industry of stone (strain) is made) of 0.25 μ m with the mixed of 50 quality %/50 quality %, forms mixture.With respect to this mixture of 100 mass parts, add after 3 mass parts hydrolysis prevent agent (two (dipropyl phenyl) carbodiimide) and mix, use biaxial extruder to carry out granulating, make so-called main sizing material.With this main sizing material and lactide acid polymer mixed, make resin combination with 40 quality %/60 quality %.
Then, use the single shaft forcing machine by the T pattern resin combination that obtains to be extruded under 220 ℃, cooling curing forms film.Under 65 ℃ of temperature with the film that obtains stretch on the MD 2.5 times, stretching on the TD after 2.8 times, under 140 ℃, heat-treat, make the reflectance coating of thickness 188 μ m.
For the reflectance coating that obtains, carry out the reflectivity before the voidage, uviolizing and the mensuration and the evaluation of the reflectivity after the uviolizing, preventing property of yellowing, hydrolytic resistance and shape-holding property.It the results are shown in table 1 and the table 2.
[embodiment 2]
In embodiment 1, except using median size is that to replace median size be the titanium oxide ( イ ペ one Network PF-740: the former industry of stone (strain) is made) of 0.25 μ m for the titanium oxide ( イ ペ one Network CR-95: the former industry of stone (strain) is made) of 0.28 μ m, similarly to Example 1, make the reflectance coating of thickness 188 μ m.To the reflectance coating that obtains, carry out similarly to Example 1 mensuration and evaluation.It the results are shown in table 1 and the table 2.
[embodiment 3]
In embodiment 1, except using median size is that to replace median size be the titanium oxide ( イ ペ one Network PF-740: the former industry of stone (strain) is made) of 0.25 μ m for the titanium oxide ( イ ペ one Network PF728: the former industry of stone (strain) is made) of 0.21 μ m, similarly to Example 1, make the reflectance coating of thickness 188 μ m.To the reflectance coating that obtains, carry out similarly to Example 1 mensuration and evaluation.It the results are shown in table 1 and the table 2.
[embodiment 4]
In embodiment 1, except using median size is that to replace median size be the titanium oxide ( イ ペ one Network PF-740: the former industry of stone (strain) is made) of 0.25 μ m for the titanium oxide ( イ ペ one Network CR50: the former industry of stone (strain) is made) of 0.25 μ m, similarly to Example 1, make the reflectance coating of thickness 188 μ m.To the reflectance coating that obtains, carry out similarly to Example 1 mensuration and evaluation.It the results are shown in table 1 and the table 2.
[embodiment 5]
Make the reflectance coating of thickness 250 μ m similarly to Example 1.To the reflectance coating that obtains, carry out similarly to Example 1 mensuration and evaluation.It the results are shown in table 1 and the table 2.
[embodiment 6]
In embodiment 1, except stretch on the MD 3 times, stretching 3.2 times on the TD replace stretching on the MD 2.5 times, stretching on the TD 2.8 times, similarly to Example 1, make the reflectance coating of thickness 80 μ m.To the reflectance coating that obtains, carry out similarly to Example 1 mensuration and evaluation.It the results are shown in table 1 and the table 2.
[embodiment 7]
In embodiment 6, except main sizing material and lactide acid polymer are replaced similarly to Example 6, making the reflectance coating of thickness 80 μ m the mixed with 40 quality %/60 quality % with the mixed of 60 quality %/40 quality %.To the reflectance coating that obtains, carry out similarly to Example 1 mensuration and evaluation.It the results are shown in table 1 and the table 2.
[comparative example 1]
The titanium oxide ( イ ペ one Network PF-740: the former industry of stone (strain) is made) that the particle and the median size of polyethylene terephthalate is 0.25 μ m with the mixed of 50 quality %/50 quality %, forms mixture.Use biaxial extruder with this compound particles granulation, make main sizing material.With this main sizing material and polyethylene terephthalate mixed, make resin combination with 40 quality %/60 quality %.Then, use the single shaft forcing machine by the T pattern resin combination that obtains to be extruded under 280 ℃, cooling curing forms film.Under 90 ℃ of temperature with the film that obtains stretch on the MD 2.5 times, stretching on the TD after 2.8 times, under 140 ℃, heat-treat, make the reflectance coating of thickness 188 μ m.For the reflectance coating that obtains, carry out similarly to Example 1 mensuration and evaluation.It the results are shown in table 1 and the table 2.
[comparative example 2]
In embodiment 1, except using median size is that to replace median size be the titanium oxide ( イ ペ one Network PF-740: the former industry of stone (strain) is made) of 0.25 μ m for the titanium oxide ( イ ペ one Network R-680: the former industry of stone (strain) is made) of 0.21 μ m, similarly to Example 1, make the reflectance coating of thickness 188 μ m.To the reflectance coating that obtains, carry out similarly to Example 1 mensuration and evaluation.It the results are shown in table 1 and the table 2.
[comparative example 3]
In embodiment 1, except using median size is that to replace median size be the titanium oxide ( イ ペ one Network PF-740: the former industry of stone (strain) is made) of 0.25 μ m for the titanium oxide ( イ ペ one Network R-630: the former industry of stone (strain) is made) of 0.24 μ m, similarly to Example 1, make the reflectance coating of thickness 188 μ m.To the reflectance coating that obtains, carry out similarly to Example 1 mensuration and evaluation.It the results are shown in table 1 and the table 2.
[embodiment 8]
According to program shown below, the reflectance coating that embodiment 1 is obtained is coated on the steel plate galvanized (thickness 0.45mm), makes reflector.That is, at first at the commercially available polyester caking agent of the surface of steel plate of applying reflectance coating coating, and to make dried caking agent thickness be about 2 μ m～4 μ m.Then, carry out the dry and heating of coated face by infrared heater and hot-blast heater, keeping the surface temperature of steel plate is 180 ℃, directly uses the roll laminating machine that reflectance coating is coated simultaneously, and cools off, and makes reflector.The reflector that obtains is reflected the mensuration and the evaluation of processibility and baffle reflection rate.It the results are shown in table 3.
[embodiment 9]
In embodiment 8, except changing to 220 ℃, the surface temperature with steel plate replaces remaining on 180 ℃, similarly to Example 8, make reflector.To the reflector that obtains, carry out similarly to Example 8 mensuration and evaluation.It the results are shown in table 3.
[table 1]
The weighting agent kind
A: イ ペ one Network PF-740: the rutile-type crystalline form titanium oxide that the former industry of stone (strain) is made
B: イ ペ one Network CR95: the rutile-type crystalline form titanium oxide that the former industry of stone (strain) is made
C: イ ペ one Network PF728: the rutile-type crystalline form titanium oxide that the former industry of stone (strain) is made
D: イ ペ one Network CR50: the rutile-type crystalline form titanium oxide that the former industry of stone (strain) is made
E: イ ペ one Network R680: the rutile-type crystalline form titanium oxide that the former industry of stone (strain) is made
F: イ ペ one Network R630: the rutile-type crystalline form titanium oxide that the former industry of stone (strain) is made
Nonactive inorganic oxide species
A: aluminum oxide
B: silicon-dioxide
C: zirconium white
[table 2]
[table 3]
By table 1 and table 2 as can be known, the reflectivity of the reflectance coating of the present invention of embodiment 1～7 is more than 96.5%, has high light reflective.In addition, the reflectivity of this reflectance coating behind the ultraviolet radiation test is more than 95%, and tone also be white, preventing property of yellowing excellence.Wherein, the initial stage reflectivity before the uviolizing of embodiment 1～3 and embodiment 5～7 is more than 97% as can be known, and the reflectivity behind the ultraviolet radiation test also is more than 95.5%, is excellent reflectivity.In addition, for hydrolytic resistance and shape-holding property, also can obtain excellent result.
On the other hand, the reflectivity of the reflectance coating of comparative example 1～3 is lower than 95% as can be known, and is keeping on the high light reflective this point, poorer than the reflectance coating of embodiment 1～7.
In addition, as shown in Table 3, the reflector of embodiment 8 can be kept necessary bounding force of processing and high light reflective.In addition, during the reflector of comparing embodiment 8 and embodiment 9, though bounding force is all very high as can be known, the reflector of embodiment 8 has been kept high light reflective, from this point of reflectivity, than the reflector excellence of embodiment 9.
[embodiment 10]
Lactide acid polymer (NW4032D: カ one ギ Le ダ ウ Port リ マ one company manufacturing with weight-average molecular weight 200,000, D body burden 1.5%) particle and median size are that the titanium oxide ( イ ペ one Network PF-728: the former industry of stone (strain) is made) of 0.21 μ m with the mixed of 50 quality %/50 quality %, forms mixture.With respect to this mixture of 100 mass parts, after adding 2.1 mass parts hydrolysis and preventing agent (two (dipropyl phenyl) carbodiimide) and mix, use biaxial extruder to carry out granulating, make so-called main sizing material.With this main sizing material and lactide acid polymer mixed, make resin combination with 70 quality %/30 quality %.
Then, use the single shaft forcing machine by the T pattern resin combination that obtains to be extruded under 220 ℃, cooling curing forms film.Under 65 ℃ of temperature with the film that obtains stretch on the MD 2.5 times, stretching on the TD after 2.8 times, under 140 ℃, heat-treat, obtain the reflectance coating of thickness 200 μ m.For the reflectance coating that obtains, carry out the mensuration and the evaluation of voidage and reflectivity.It the results are shown in table 4 and the table 5.
[embodiment 11]
(being used for the making of the resin combination of A layer)
Lactide acid polymer (NW4032D: カ one ギ Le ダ ウ Port リ マ one company manufacturing with weight-average molecular weight 200,000, D body burden 1.5%) particle and median size are that the titanium oxide ( イ ペ one Network PF-740: the former industry of stone (strain) is made) of 0.25 μ m with the mixed of 50 quality %/50 quality %, forms mixture.With respect to this mixture of 100 mass parts, add after 2.1 mass parts hydrolysis prevent agent (two (dipropyl phenyl) carbodiimide) and mix, use biaxial extruder to carry out granulating, make so-called main sizing material.With this main sizing material and lactide acid polymer mixed, make resin combination A with 70 quality %/30 quality %.
(being used for the making of the resin combination of B layer)
Lactide acid polymer (NW4032D: カ one ギ Le ダ ウ Port リ マ one company manufacturing with weight-average molecular weight 200,000, D body burden 1.5%) particle and median size are that the titanium oxide ( イ ペ one Network PF-728: the former industry of stone (strain) is made) of 0.21 μ m with the mixed of 50 quality %/50 quality %, forms mixture.With respect to this mixture of 100 mass parts, add after 2.1 mass parts hydrolysis prevent agent (two (dipropyl phenyl) carbodiimide) and mix, use biaxial extruder to carry out granulating, make so-called main sizing material.With this main sizing material and lactide acid polymer mixed, make resin combination B with 70 quality %/30 quality %.
(making of film)
With resin combination A and resin combination B supply to respectively 2 forcing machine A and B separately in the middle of.Promptly, resin combination A is supplied among the forcing machine A that is heated to 220 ℃, resin combination B is supplied among the forcing machine B that is heated to 220 ℃, use the T pattern that the resin combination A of molten state and the resin combination B of molten state are extruded into sheet, and become A layer/B layer/A layer
3 layersStructure, cooling curing forms film.
Under 65 ℃ of temperature with the film that obtains stretch on the MD 2.5 times, on TD, stretch 2.8 times.Then, implement thermal treatment down, make thickness 200 μ m (A layer: 18 μ m, B layer: reflectance coating 164 μ m) at 140 ℃.
For the reflectance coating that obtains, carry out similarly to Example 10 mensuration and evaluation.It the results are shown in table 4 and table 5.
[embodiment 12]
In embodiment 11, except using median size is titanium oxide (the イ ペ one Network PF-690: the former industry of stone (strain) manufacturing of 0.21 μ m, content of niobium 500ppm is following) replace median size be 0.21 μ m titanium oxide ( イ ペ one Network PF-728: the former industry of stone (strain) is made) in addition, similarly to Example 11, make the reflectance coating of thickness 200 μ m.
To the reflectance coating that obtains, carry out similarly to Example 11 mensuration and evaluation.It the results are shown in table 4 and table 5.
[embodiment 13]
In embodiment 10, except using median size is titanium oxide (the イ ペ one Network CR50-2: the former industry of stone (strain) manufacturing of 0.25 μ m, content of niobium 500ppm is following) replace median size be 0.21 μ m titanium oxide ( イ ペ one Network PF-728: the former industry of stone (strain) is made) in addition, similarly to Example 10, make the reflectance coating of thickness 200 μ m.
To the reflectance coating that obtains, carry out similarly to Example 10 mensuration and evaluation.It the results are shown in table 4 and table 5.
[embodiment 14]
In embodiment 10, except using median size is titanium oxide (the イ ペ one Network CR63: the former industry of stone (strain) manufacturing of 0.21 μ m, content of niobium 500ppm is following) replace median size be 0.21 μ m titanium oxide ( イ ペ one Network PF-728: the former industry of stone (strain) is made) in addition, similarly to Example 10, make the reflectance coating of thickness 200 μ m.
To the reflectance coating that obtains, carry out similarly to Example 10 mensuration and evaluation.It the results are shown in table 4 and table 5.
[embodiment 15]
In embodiment 11, except using median size is titanium oxide (the イ ペ one Network CR50-2: the former industry of stone (strain) manufacturing of 0.25 μ m, content of niobium 500ppm is following) to replace median size be the titanium oxide ( イ ペ one Network PF-740: the former industry of stone (strain) is made) of 0.25 μ m, in addition, using median size is titanium oxide (the イ ペ one Network PF-671: the former industry of stone (strain) manufacturing of 0.21 μ m, content of niobium 500ppm is following) replace median size be 0.21 μ m titanium oxide ( イ ペ one Network PF-728: the former industry of stone (strain) is made) in addition, similarly to Example 11, make the reflectance coating of thickness 200 μ m.
To the reflectance coating that obtains, carry out similarly to Example 11 mensuration and evaluation.It the results are shown in table 4 and table 5.
[table 4]
The weighting agent kind
B: イ ペ one Network PF728: the rutile-type crystalline form titanium oxide that the former industry of stone (strain) is made
C: イ ペ one Network PF740: the rutile-type crystalline form titanium oxide that the former industry of stone (strain) is made
D: イ ペ one Network PF690: the rutile-type crystalline form titanium oxide that the former industry of stone (strain) is made
E: イ ペ one Network CR50-2: the rutile-type crystalline form titanium oxide that the former industry of stone (strain) is made
F: イ ペ one Network CR63: the rutile-type crystalline form titanium oxide that the former industry of stone (strain) is made
G: イ ペ one Network PF671: the rutile-type crystalline form titanium oxide that the former industry of stone (strain) is made
Nonactive inorganic oxide species
A: aluminum oxide
B: silicon-dioxide
C: zirconium white
[table 5]
By table 4 and table 5 as can be known, the reflectivity of the reflectance coating of embodiment 10～15 is more than 96%, has high light reflective.In addition, the surface treatment amount of using nonactive inorganic oxide is that the reflectivity of reflectance coating of embodiment 10～12 of the titanium oxide of 3 quality %～9 quality % is more than 97.5%, is the high light reflective of reflectance coating demonstration of the embodiment 13～15 of the titanium oxide 2.5 below than using surface treatment amount.
In addition and since the reflectance coating of embodiment 10～13 be with aliphatic polyester-based resin as base resin, therefore, can not pass in time in use and produce yellowing or reflectivity is reduced.
That is,, can realize having excellent light reflective, and can not pass in time in use and produce yellowing or light reflective is reduced according to the present invention, and the reflectance coating of shape-holding property excellence.In addition,, when landfill disposal, can decompose, can not produce the problem on discarded by microorganism etc. because this reflectance coating has biological degradability.If use this reflectance coating, can obtain having the reflector of excellent above-mentioned characteristics such as light reflective.
Industrial applicibility
The present invention can use in reflecting plates such as liquid crystal indicator, illumination instrument, lighting billboard etc. In the reflectance coating that uses.
Claims (6)
1. aliphatic polyester-based resin reflective film, this reflectance coating is formed by resin combination, and has the space in inside, its voidage is below 50%, described resin combination contains that specific refractory power is lower than 1.52 aliphatic polyester-based resin and based on the microgranular weighting agent of titanium oxide, wherein, the content of niobium in this titanium oxide is below the 500ppm.
2. the described aliphatic polyester-based resin reflective film of claim 1, wherein, at least a nonactive inorganic oxide that the surface of above-mentioned titanium oxide is selected from silicon-dioxide, aluminum oxide and the zirconium white coats.
3. claim 1 or 2 described aliphatic polyester-based resin reflective films, wherein, in the aliphatic polyester resin composition that contains fine powdered weighting agent and aliphatic polyester-based resin, the content of above-mentioned fine powdered weighting agent is 10 quality %～60 quality %.
4. any one described aliphatic polyester-based resin reflective film in the claim 1～3, wherein, above-mentioned aliphatic polyester-based resin is a lactide acid polymer.
5. any one described aliphatic polyester-based resin reflective film in the claim 1～4, this reflectance coating be fusion system film is contained the aliphatic polyester resin composition of aliphatic polyester-based resin and fine powdered weighting agent and the film that obtains at least at stretch film more than 1.1 times of single shaft direction.
6. a reflector wherein has any one described aliphatic polyester-based resin reflective film in the claim 1～5.
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| JP2004212511 | 2004-07-21 | ||
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| CN102453339A (en) * | 2010-11-01 | 2012-05-16 | 宝纬科技有限公司 | Preparation method of reflective plate by using composite material |
| CN103777261B (en) * | 2014-02-10 | 2016-03-02 | 张家港康得新光电材料有限公司 | A kind of reflectance coating |
| CN108912460A (en) * | 2018-07-26 | 2018-11-30 | 山东圣和塑胶发展有限公司 | The shrink film of antiultraviolet raising shelf-life |
| CN109627733B (en) * | 2018-12-14 | 2021-01-15 | 金旸（厦门）新材料科技有限公司 | High-whiteness and high-toughness PC composition and preparation method thereof |
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