CN101528819A - Polyvinyl acetal sheet and process for production thereof - Google Patents

Polyvinyl acetal sheet and process for production thereof Download PDF

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Publication number
CN101528819A
CN101528819A CNA2007800390000A CN200780039000A CN101528819A CN 101528819 A CN101528819 A CN 101528819A CN A2007800390000 A CNA2007800390000 A CN A2007800390000A CN 200780039000 A CN200780039000 A CN 200780039000A CN 101528819 A CN101528819 A CN 101528819A
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China
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polyvinyl acetal
sheet
softening agent
particle
laminated glass
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Chinese (zh)
Inventor
辻强志
香坂昌信
吉井茂晴
齐藤智夫
增子芳弘
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Denka Co Ltd
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Denki Kagaku Kogyo KK
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Publication of CN101528819A publication Critical patent/CN101528819A/en
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Abstract

The invention provides a polyvinyl acetal sheet which is useful in producing laminated glass and excellent in the adhesion to glass and which permits easy control of adhesiveness and exhibits little discoloration, high transparency, and excellent penetration resistance even under high-temperature conditions; a process for production of the same; and a process for production of polyvinyl acetal particles to be used in the sheet. The polyvinyl acetal sheet is characterized by having a porosity of 60 to 85% and by being produced by molding polyvinyl acetal particles having a degree of acetalization of 75.0 to 84.0% by mass into a film. The polyvinyl acetal particles are preferably produced by a process of subjecting 100 parts by mass of polyvinyl alcohol and 40 to 75 parts by mass of an aldehyde to acetalization in the presence of an acid catalyst at a reaction temperature of 20 to 60 DEG C which process comprises feeding polyvinyl alcohol, an aldehyde and an acid catalyst into a reactor to conduct acetalization, discharging the reaction mixture from the reactor when the degree of acetalization has reached at least 13% by mass, and aging the discharged reaction mixture.

Description

Polyvinyl acetal sheet and manufacture method thereof
Technical field
The manufacture method that the present invention relates to polyvinyl acetal sheet, its manufacture method and be used for their polyvinyl acetal particle.
Background technology
Laminated glass normally make the laminated glass-use intermediate coat that forms by thermoplastic resins such as urethane or vinyl-vinyl-acetic ester multipolymer, polyvinyl acetal resins (following also be called for short " intermediate coat ") between two blocks of sheet glass and glass (for example with reference to patent documentation 1 and 2).
Particularly polyvinyl acetal resin is widely used as the raw material of intermediate coat, coating, caking agent etc. as the laminated glass of shatter proof glass.Polyvinyl acetal resin can be by the whole bag of tricks manufacturing, but mainly makes by the method that is called the water medium method, and this method is as described below: add aldehyde in the aqueous solution of polyvinyl alcohol in the presence of acid catalyst, the beginning acetalation; Generate precipitation when carrying out acetalation, in nonhomogeneous system, react afterwards.
Aldehyde in the aforesaid method adds and generally carries out under the lesser temps below 20 ℃, then intensification and carrying out slaking reaction more than 40 ℃.Reaction neutralizes by alkali after finishing.In order to remove impurity, wash repeatedly and dewater, behind the purifying, dry and form goods.The manufacture method of polyvinyl acetal is gone back manufacture method such as known solvent method, homogeneous system method except above-mentioned water medium method.
The polyvinyl acetal resin that manufacture method by above-mentioned water medium method obtains can be used to the manufacturing of laminated glass-use intermediate coat well.This laminated glass is widely used in the peristomes such as window of various Transport Machinery such as automobile, flyer or buildings.The laminated glass of window glass that is used as automobile or buildings also requires no gonorrhoea and painted etc. and transparent high fundamental property as glass certainly except security and anti-theft.
But owing to be difficult to obtain transparent intermediate coat fully, existing laminated glass has problems aspect transparent.
As the transparent main reasons for decrease that makes intermediate coat, can exemplify that impurity in the starting material in the manufacturing processed is sneaked into or thermolysis, the oxygenolysis of material resin.If material resin thermolysis or oxygenolysis, then intermediate coat is colored as light yellowly, and the transparency significantly descends.
If particularly use the too high material resin of void content, then material resin and softening agent may be in hopper aggegation and form the granulous piece.Also can't be even the piece of this material resin and softening agent is conducted to machine barrel (cartridge heater) by thorough mixing, thermolysis can take place in the part that does not contact softening agent of material resin sometimes.
For fear of this problem, also adopt and to be conducted to the method for machine barrel after material resin and the plasticizer particleization in advance, but thermolysis takes place in the thermal process that material resin is stood in this case sometimes also still can be because of granulating the time.
In addition, laminated glass possesses following performance: though glass in that to be subjected to impacting the back damaged, the intermediate coat between glass is cracky not also, and absorbs and impact.Therefore, rammer is not easy to run through laminated glass.In addition, after breakage, still adhere to intermediate coat, so the fragment of glass can not disperse yet, thereby can not cause serious injury the human body that is positioned at Transport Machinery or buildings or implements etc. by intermediate coat adherent glass.
So; in order to give human body or the safer protection of implements at impact from the outside; with regard to above-mentioned situation, the intermediate coat that is used for laminated glass with the cementability of glass and the anti-performance that need have the purposes that adapts to employed laminated glass aspect the intensity that runs through.
As good polyvinyl acetal resin and the manufacture method thereof of cementability that is used for laminated glass-use intermediate coat etc., known various prior aries.
For example, in the patent documentation 1,, bonding force good as cementability adjusted and stable laminated glass-use intermediate coat easily, knownly contains the metal of divalent and makes the polyvinyl acetal resin of its content below 30ppm.The thermotolerance deficiency of this polyvinyl acetal resin is configured as sheet and makes under the situation that polyvinyl acetal sheet uses, if the envrionment temperature height, then anti-penetrability descends, so also have the leeway of improvement, needs further to improve.
Patent documentation 1: the Japanese Patent spy opens the 2000-1514 communique
Patent documentation 2: Japanese patent laid-open 11-349769 communique
The announcement of invention
The object of the present invention is to provide when being used to laminated glass etc., good with the cementability of glass, the adjustment of cementability is easy, degree of staining is low, the transparency is high and at high temperature also have good anti-polyvinyl acetal sheet, its manufacture method that runs through performance, be used for this sheet material resin (the following polyvinyl acetal particle that also claims) manufacture method and adopt this sheet the laminated glass-use intermediate coat, adopt the laminated glass of this intermediate coat.
The present invention has carried out conscientiously research back discovery to achieve these goals, following polyvinyl acetal particle is configured as sheet and sheet can realize above-mentioned purpose: acetalizing degree is 75.0～84.0 quality %, and specific polyvinyl acetal particle with void content of 60～85%, in this polyvinyl acetal particle, better be the following polyethylene alcohols and aldehydes is reacted under given conditions and the polyvinyl acetal particle.
That is, the present invention has the technology contents of following characteristics.
(1) polyvinyl acetal sheet is characterized in that, acetalizing degree is that 75.0～84.0 quality % and void content are that 60～85% polyvinyl acetal particle is configured as sheet and forms.
(2) as above-mentioned (1) described polyvinyl acetal sheet, wherein, the polyvinyl acetal particle is following to be obtained: make 100 mass parts polyvinyl alcohol and 40～75 mass parts aldehyde in the presence of an acidic catalyst when 20～60 ℃ temperature is carried out acetalation, polyvinyl alcohol, aldehyde and an acidic catalyst are conducted to reactor carry out acetalation, after the acetalizing degree of the polyvinyl acetal that generates reaches at least 13 quality %, discharge reactant from this reactor, make the reactant that is discharged from carry out slaking reaction.
(3) as above-mentioned (2) described polyvinyl acetal sheet, wherein, reactor is the reactor that has been full of reaction solution in the container.
(4) as above-mentioned (2) or (3) described polyvinyl acetal sheet, wherein, the stirring power with unit volume 0.5～1.5kw in the reactor stirs.
(5) as each the described polyvinyl acetal sheet in above-mentioned (1)～(4), wherein, aldehyde comprises butyraldehyde at least.
(6), wherein,, comprise 10～50 mass parts softening agent with respect to 100 mass parts polyvinyl acetal particles as each the described polyvinyl acetal sheet in above-mentioned (1)～(5).
(7) with each the described polyvinyl acetal sheet in above-mentioned (1)～(6) more than 2 overlapping and duplexer.
(8) each the described polyvinyl acetal sheet in employing above-mentioned (1)～(7) or the laminated glass-use intermediate coat of duplexer.
(9) manufacture method of above-mentioned (1) described polyvinyl acetal sheet wherein, is used the sheet manufacturing installation, supplies with polyvinyl acetal particle and softening agent and carries out extrusion molding; Described manufacturing installation comprises screw-type extruder with polyvinyl acetal particle supply unit and softening agent supply unit and the reeling machine with T mould and grain roller, and with the distance to screw front end is made as S from polyvinyl acetal particle supply unit in the described screw-type extruder, will be from polyvinyl acetal particle supply unit when the distance to the softening agent supply unit is made as L, L=0.05～0.3.
(10), wherein, supply with described softening agent continuously with the feed rate of 20～50kg/h with respect to the feed rate of the described polyvinyl acetal particle of every 100kg/h as the manufacture method of above-mentioned (9) described polyvinyl acetal sheet.
(11) as the manufacture method of above-mentioned (9) or (10) described polyvinyl acetal sheet, wherein, the feed rate of the described polyvinyl acetal particle that will represent with kg/h is made as the Q that represents with kg/h with the feed rate sum of the described softening agent of representing with kg/h, when the rotating speed of the described screw rod that will represent with r.p.m. is made as Ns, 0.2≤Q/Ns≤0.5.
(12) as the manufacture method of each the described polyvinyl acetal sheet in above-mentioned (9)～(11), wherein, described softening agent is a Triethyleneglycol di 2 ethylhexanoate.
(13) as the manufacture method of each the described polyvinyl acetal sheet in above-mentioned (9)～(12), wherein, the opening thickness of described T mould is 1～1.6 times of thickness of the polyvinyl acetal sheet of manufacturing.
(14) as the manufacture method of each the described polyvinyl acetal sheet in above-mentioned (9)～(13), wherein, described grain roller are to have with the diameter of following formula (1) expression and 2 grain roller that are arranged in parallel of surfaceness, make the polyvinyl acetal particle that is extruded from described T mould by carrying out surface treatment between these grain roller;
r 1/ r 2＞0.3 and 3.0＞Rz 1/ Rz 2＞1.2 (1)
In the formula, r 1The diameter of representing first grain roller, r 2The diameter of representing second grain roller, Rz 1The surfaceness Rz that represents first grain roller, Rz 2The surfaceness Rz that represents second grain roller.
(15) adopt the laminated glass-use intermediate coat of the polyvinyl acetal sheet that obtains by each the described manufacture method in above-mentioned (9)～(14).
(16) laminated glass of employing above-mentioned (8) or (15) described laminated glass-use intermediate coat.
If employing the present invention, then can be provided in when being used to laminated glass etc., good with the cementability of glass, the adjustment of cementability is easy, degree of staining is low, transparency height and quality is even, at high temperature also have good anti-polyvinyl acetal sheet, its manufacture method that runs through performance, be used for this sheet the polyvinyl acetal particle manufacture method and adopt this sheet the laminated glass-use intermediate coat, adopt the laminated glass of this intermediate coat.
The simple declaration of accompanying drawing
Fig. 1 is the synoptic diagram (L=0.05) of position relation of material resin supply unit, softening agent supply unit, the screw rod of the machine barrel (cartridge heater) of the screw-type extruder that uses among the present invention of expression.
Fig. 2 is the synoptic diagram (L=0.3) of position relation of material resin supply unit, softening agent supply unit, the screw rod of the machine barrel (cartridge heater) of the screw-type extruder that uses among the present invention of expression.
Fig. 3 is the synoptic diagram (S/L=1.25) of temperature-controlled process that is used for illustrating the machine barrel of screw-type extruder.
Fig. 4 is the synoptic diagram (S/L=10) of temperature-controlled process that is used for illustrating the machine barrel of screw-type extruder.
The explanation of symbol
A: machine barrel, A 1: first delivery section, A 2: compression fusing department, A 3: second delivery section, B: material resin supply unit, C: softening agent supply unit, D: screw rod, E: venting hole, P: screw front end, L: distance from material resin supply unit B to softening agent supply unit C.
The best mode that carries out an invention
Polyvinyl acetal sheet of the present invention is by being that 75.0～84.0 quality % and void content have 60～85% specific polyvinyl acetal particle to be configured as sheet to make with acetalizing degree.Among the present invention used polyvinyl acetal particle be in the presence of an acidic catalyst, make the polyethylene alcohols and aldehydes carry out acetalation and the polyvinyl acetal particle.
It is preferred 1000～2500, particularly preferred 1500～2000 that polyvinyl alcohol better is to use mean polymerisation degree, and saponification deg is that preferred 80 moles of % are above, particularly preferred polyvinyl alcohol more than 90 moles.
If use the polyvinyl alcohol of saponification deg less than 80%, then with the intermiscibility variation of softening agent.Therefore, softening agent may travel to the surface of intermediate coat and ooze out perhaps crystallization (ooze and move).
Among the present invention, from the angle of usability, polyvinyl alcohol better is that the aqueous solution of making 3～15 quality % uses.
The consumption of the aldehyde in the acetalation is according to getting final product as the acetalizing degree of the polyvinyl acetal of target is suitably selected, if adopt preferred 40～75 mass parts, particularly preferred 43～65 mass parts with respect to 100 mass parts polyvinyl alcohol, then acetalation is carried out efficiently, is ideal therefore.In addition, if the amount that makes butyraldehyde more than the preferred 30 quality % of all aldehyde that use, more than the particularly preferred 40 quality %, therefore the then anti-penetrability and the raisings such as cementability, flexibility of the sheet of gained are ideal.
As above-mentioned an acidic catalyst, be not particularly limited, can use for example inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, organic acids such as acetate, tosic acid.The general suitable interpolation of these an acidic catalysts and make the pH of reaction solution reach preferred 0.3～2, particularly preferred 0.4～1 to get final product.
The aldehyde that uses in the manufacturing of polyvinyl acetal particle can also as required and be used other aldehyde except that butyraldehyde.
As above-mentioned other aldehyde, for example have formaldehyde, paraformaldehyde, acetaldehyde, paraldehyde, propionic aldehyde, valeral, hexanal, enanthaldehyde, 2-ethyl hexanal, hexamethylene aldehyde, furfural, oxalic dialdehyde, glutaraldehyde, phenyl aldehyde, 2-tolyl aldehyde, 3-tolyl aldehyde, 4-tolyl aldehyde, p-Hydroxybenzaldehyde, m-hydroxybenzaldehyde, phenylacetic aldehyde, beta-phenyl propionic aldehyde etc., wherein can preferably use acetaldehyde, hexanal.
Polyvinyl acetal particle used among the present invention gets by the polyethylene alcohols and aldehydes is carried out acetalation in the presence of an acidic catalyst, better is following the reaction.That is, will be full of reactor by the reaction solution that polyvinyl alcohol, aldehyde and an acidic catalyst form, the beginning acetalation resupplies reaction solution, better is to supply with continuously.
Then, the acetalizing degree of the polyvinyl acetal of generation reach at least 13 quality %, better be at least 20 quality % after, discharge reactant from this reactor, better be to discharge continuously.Then, make the reactant that is discharged from carry out slaking reaction, make acetalizing degree rise to 75～84%, slaking reaction better is to carry out in other reactor.
In order to make not ingress of air of reaction solution, employed reactor better is the reactor that has been full of reaction solution in the container among the present invention.
If the temperature of above-mentioned acetalation is made as 20～60 ℃, better is 30～45 ℃, then can successfully carry out acetalation suppressing the adherent while of resin to the inwall and the stirring rake of reactor.Above-mentioned reactor is made as unit volume 0.5～1.5kw, when better being 0.6～1.2kw, reaction solution can be mixed at stirring power, and the void content that can make the polyvinyl acetal of gained is 60～85%.
If the temperature of the slaking reaction of the reactant that is discharged from this reactor is made as temperature of reaction～55 ℃ of temperature of reaction～60 ℃ of preferred reaction solution, particularly preferred reaction solution, when slaking reaction was successfully carried out, the void content that can make the polyvinyl acetal of gained was 60～85%.In addition, be 75.0～84.0 quality %, better be 78.0～83.0 quality %, the Combination with softening agent is improved by the acetalizing degree that makes polyvinyl acetal.
Under the situation of the acetalizing degree less than 75.0 quality % of polyvinyl acetal, the contained hydroxyl of polyvinyl acetal increases, and the water tolerance of the intermediate coat of gained descends.Therefore, when making laminated glass, airborne moisture penetration may take place and the white situation of mist appears in the edge portion of laminated glass.In addition, the acetalizing degree of polyvinyl acetal is under the situation more than the 84.0 quality %, and the hardness of polyvinyl acetal raises, and the resistance to breakage of the laminated glass of gained and anti-penetrability may descend.
The above-mentioned reactant through slaking that contains polyvinyl acetal stops acetalation by adding neutralizing agent.Neutralizing agent is not particularly limited, and can use for example alkaline neutralisers such as sodium hydroxide, potassium hydroxide, ammonia, sodium acetate, yellow soda ash, sodium bicarbonate, salt of wormwood, alkylene oxides such as oxyethane, Racemic glycidol ethers such as ethylene glycol diglycidylether.
Reactant after the neutralizing treatment obtains the polyvinyl acetal particle through filtration, washing, drying process.The mean polymerisation degree of this polyvinyl acetal particle better is 1000～2500, and good especially is 1500～2000.In addition, the contained remaining ethanoyl of this polyvinyl acetal particle better is 0.5～3 quality %, and good especially is 0.8～2 quality %.
In addition, the polyvinyl acetal particle with the primary particle aggegation the state of offspring generate, the size distribution of its particle better be 0.1～1.0mm, good especially be that 0.15～0.5mm has peak value.Under the little situation of this scope of peakedness ratio, itself disperses particle, and difficulty becomes in the processing.Also have, the size distribution among the present invention is measured with the different sieve of mesh according to JIS Z 8815 " size analysis general rule ".
Among the present invention, the void content of polyvinyl acetal particle is 60～85%.The void content of polyvinyl acetal particle is the sign of the state of the offspring that generated, if void content diminishes, then the sheet that is obtained by the mixture of polyvinyl acetal particle and additive etc. becomes inhomogeneous, and existing is shaped adds the anti-situation that runs through degradation that produces insolubles or sheet man-hour on sheet.Its reason is considered to, if void content diminishes, then the Combination of additives such as polyvinyl acetal particle and softening agent descends.On the other hand, if the void content of polyvinyl acetal particle is too high, then the volume density of polyvinyl acetal particle diminishes, and the processing aspect is not good.Wherein, the void content of polyvinyl acetal particle better is 65～85%, and good especially is 70～85%.When adjusting void content, temperature of reaction and the stirring power of adjusting acetalation get final product.
Void content among the present invention (%) is meant that void volume in the particle is with respect to particle volumetrical ratio.Void volume in the particle is for example used automatic void content meter (for example, the (Island Jin System of Shimadzu Scisakusho Ltd does society of institute) system, Autopore IV9520) try to achieve with mensuration pressure by mercury penetration method from 0.003MPa to 34.5MPa.
When forming polyvinyl acetal sheet, better be to use softening agent and the UV light absorber that adopts as required, antioxidant, bonding force to adjust various additives such as agent, coupling agent, tensio-active agent, thermo-stabilizer, infrared absorbent, fluorescent agent, tinting material, dewatering agent, defoamer, antistatic agent, fire retardant by the polyvinyl acetal particle that obtains as mentioned above.These additives can use more than a kind or 2 kinds.
As above-mentioned softening agent, can use the softening agent that is usually used in plastics, wherein, the preferred ester plasticizer that uses intramolecularly to have ehter bond among the present invention.
For example, can exemplify ethylene glycol bisthioglycolate-2 Ethylbutanoic acid ester, 1, ammediol-2 Ethylbutanoic acid ester, 1,4-propylene glycol-2 Ethylbutanoic acid ester, 1,2-propylene glycol-2 Ethylbutanoic acid ester, glycol ether-2 Ethylbutanoic acid ester, glycol ether-2-ethylhexanoate, triglycol-2 Ethylbutanoic acid ester, triglycol-2-ethylhexanoate, Tetraglycol 99-2 Ethylbutanoic acid ester etc.They may be used alone, two or more kinds can also be used.
Among the present invention, particularly when using Triethyleneglycol di 2 ethylhexanoate, can make bonding force raising with glass.
Softening agent, is not particularly limited according to mean polymerisation degree, acetalizing degree and the remaining acetyl base unit weight etc. of polyvinyl acetal particle and different with respect to the addition of polyvinyl acetal particle.Wherein, the addition of softening agent better is 10～50 mass parts with respect to 100 mass parts polyvinyl acetal particles, and good especially is 20～45 mass parts.If in this scope, then can when keeping melt-shaping, the anti-penetrability of the sheet of gained be improved.
As above-mentioned UV light absorber, can use the UV light absorber that is usually used in plastics.For example, benzotriazole category UV light absorber, hindered amines UV light absorber, benzoates UV light absorber etc. are arranged.
As above-mentioned benzotriazole category UV light absorber, 2-(5-methyl-2-hydroxy phenyl) benzotriazole, 2-[2-hydroxyl-3 are arranged, two (the α of 5-, α '-dimethyl benzyl) phenyl]-2H-benzotriazole, 2-(3,5-di-t-butyl-2-hydroxy phenyl) benzotriazole, 2-(the 3-tertiary butyl-5-methyl-2-hydroxy phenyl)-5-chlorobenzotriazole, 2-(3,5-di-t-butyl-5-methyl-2-hydroxy phenyl)-5-chlorobenzotriazole, 2-(3,5-two tert-pentyls-2-hydroxy phenyl) benzotriazole, 2-(2 '-hydroxyl-5 '-uncle's octyl phenyl) benzotriazole etc.
As above-mentioned hindered amines UV light absorber, have 2,2,6,6-tetramethyl--4-piperidyl benzoic ether, two (2,2,6,6-tetramethyl--4-piperidyl) sebate, two (1,2,2,6,6-pentamethyl--4-piperidyl)-2-(3, the 5-di-tert-butyl-4-hydroxyl benzyl)-2-n-butylmalonic acid ester, 4-(3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyloxy)-1-(2-(3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyloxy) ethyl)-2,2,6,6-tetramethyl piperidine etc.
As above-mentioned benzoates UV light absorber, have 2,4-di-tert-butyl-phenyl-3,5-di-tert-butyl-4-hydroxybenzoic acid ester, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoic acid ester etc.
Above-mentioned UV light absorber can be used separately, perhaps is used in combination more than 2 kinds.The incorporation of UV light absorber is 10～100000ppm to haggle over respect to the quality criteria of polyvinyl acetal particle, and good especially is 100～10000ppm.If in this scope, then can in the control manufacturing cost, the photostabilization of the sheet of gained be improved.
As above-mentioned antioxidant, phenol antioxidant, Phosphorus antioxidant, sulphur class antioxidant etc. are for example arranged, wherein better be phenol antioxidant, good especially is alkyl-substituted phenols class antioxidant.
As above-mentioned phenol antioxidant, alkyl-substituted phenols compounds, acrylic ester compound are arranged, contain the phenolic compound of triazinyl etc.
As the abovementioned alkyl substituted phenol compound, have 2, the 6-di-tert-butyl-4-methy phenol, 2,6-di-t-butyl-4-ethylphenol, octadecyl-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester, 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol), 4,4 '-butylidene two (4-methyl-6-tert butyl phenol), 4,4 '-butylidene two (6-tertiary butyl meta-cresol), 4,4 '-thiobis (3 methy 6 tert butyl phenol), two (3-cyclohexyl-2-hydroxy-5-methyl base phenyl) methane, 3, two (the 2-(3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy)-1 of 9-, the 1-dimethyl ethyl)-2,4,8,10-four oxaspiros [5,5] undecane, 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, four (methylene radical-3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid ester group) methane, triglycol two (3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester) etc.
As the aforesaid propylene acid esters compound, the 2-tertiary butyl-6-(the 3-tertiary butyl-2-hydroxy-5-methyl base benzyl)-4-aminomethyl phenyl acrylate, 2 is arranged, 4-two tert-pentyls-6-(1-(3,5-two tert-pentyls-2-hydroxy phenyl) ethyl) phenyl acrylate etc.
As the above-mentioned phenolic compound that contains triazinyl, 6-(4-hydroxyl-3,5-di-tert-butyl amido)-2 is arranged, the two hot sulfenyl-1,3,5-triazines of 4-, 6-(4-hydroxyl-3,5-dimethyl benzene amido)-2, the two hot sulfenyls-1,3 of 4-, 5-triazine, 6-(4-hydroxy-3-methyl-5-tert.-butylbenzene amido)-2, the two hot sulfenyls-1,3 of 4-, 5-triazine, the hot sulfenyl-4 of 2-, two (3,5-di-t-butyl-4-oxygen anilino)-1 of 6-, 3,5-triazine etc.
As above-mentioned Phosphorus antioxidant, single phosphite ester compound, diphosphorous acid ester compound are arranged.
As single phosphite ester compound, the triphenyl phosphorous acid ester is arranged, phenylbenzene isodecyl phosphorous acid ester, phenyl diiso decyl phosphorous acid ester, three (nonyl phenyl) phosphorous acid ester, three (dinonyl phenyl) phosphorous acid ester, three (the 2-tertiary butyl-4-aminomethyl phenyl) phosphorous acid ester, three (cyclohexyl phenyl) phosphorous acid ester, 2,2-methylene-bis (4, the 6-di-tert-butyl-phenyl) octyl group phosphorous acid ester, 9, the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound, 10-(3, the 5-di-tert-butyl-4-hydroxyl benzyl)-9, the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound, 10-oxygen in last of the ten Heavenly stems base-9, the 10-dihydro-9-oxy is assorted-the 10-phospho hetero phenanthrene etc.
As above-mentioned diphosphorous acid ester compound, have 4,4 '-butylidene two (3-methyl-6-tert butyl phenyl-two-tridecyl phosphorous acid ester), 4, two (the phenyl-two-alkyl (C12～C15) phosphorous acid ester), 4 of 4 '-isopropylidene, 4 '-isopropylidene two (phenylbenzene one alkyl (C12～C15) phosphorous acid ester), 1,1,3-three (2-methyl-4-two-tridecyl phosphorous acid ester group-5-tert-butyl-phenyl) butane, four (2, the 4-di-tert-butyl-phenyl)-4,4 '-biphenylene phosphorous acid ester etc.Wherein, better be single phosphite ester compound.
As above-mentioned sulphur class antioxidant, for example have 3,3 '-thiodipropionate dilauryl, 3,3 '-thio-2 acid distearyl ester, 3,3 '-thio-2 acid lauryl stearyl, tetramethylolmethane four (β-lauryl thiopropionate), 3, two (the 2-dodecyl sulphur ethyls)-2 of 9-, 4,8,10-four oxaspiros [5,5] undecane etc.
Above-mentioned antioxidant can use separately, perhaps is used in combination more than 2 kinds.The incorporation of antioxidant better is 0.001～5 mass parts with respect to 100 mass parts polyvinyl acetal particles, and good especially is 0.01～1 mass parts.If in this scope, then can be in the control manufacturing cost, thermal degradation when when preventing melt-shaping and the acid number deterioration that causes with contacting of extraneous air.
Adjust agent as above-mentioned bonding force, be not particularly limited, can exemplify an alkali metal salt or alkaline earth salt, the modified silicon oil etc. of organic acid an alkali metal salt for example or alkaline earth salt, mineral acid.
An alkali metal salt or the alkaline earth salt of these organic acids or mineral acid may be used alone, two or more kinds can also be used.
As organic acid, can exemplify carboxylic acids such as for example sad, caproic acid, butyric acid, acetate, formic acid etc.As mineral acid, can exemplify for example hydrochloric acid, nitric acid etc.As an alkali metal salt or the alkaline earth salt of above-mentioned organic acid or mineral acid, can exemplify sylvite, sodium salt, magnesium salts of organic acid for example or mineral acid etc.
In an alkali metal salt or alkaline earth salt of above-mentioned organic acid or mineral acid, can preferably use carbon number better be 2～16, good especially be alkaline earth salts such as an alkali metal salts such as 2～10 organic acid sylvite or magnesium salts.
As the organic acid of carbon number 2～16, better be an alkali metal salt or the alkaline earth salt of carboxylic acid, can exemplify for example potassium acetate, magnesium acetate, potassium propionate, propionic acid magnesium, 2 Ethylbutanoic acid potassium, 2 Ethylbutanoic acid magnesium, 2 ethyl hexanoic acid potassium, 2 ethyl hexanoic acid magnesium etc.
An alkali metal salt of above-mentioned organic acid or mineral acid or the incorporation of alkaline earth salt are not particularly limited, with respect to 100 mass parts polyvinyl acetal particles better is 0.0001～1 mass parts, good especially is 0.001～0.5 mass parts, is more preferably 0.01～0.2 mass parts.If in this scope, then can be under the situation of the transparency of not destroying laminated glass, the cementability of trim plate.
As above-mentioned modified silicon oil, so long as general make the compound that will carry out modification and polysiloxane reaction and modified silicon oil get final product.For example, can exemplify epoxy group(ing) modified silicon oil, ether modified silicon oil, ester modified silicone oil, amine modified silicon oil, carboxy-modified silicone oil etc.They may be used alone, two or more kinds can also be used.
The molecular weight of above-mentioned modified silicon oil is not particularly limited, and number-average molecular weight better is 800～5000, and good especially is 1500～4000.If in this scope, then can keep the intermiscibility with polyvinyl acetal, modified silicon oil is evenly dispersed on the sheet.
The usage quantity of modified silicon oil is not particularly limited, and better is 0.01～0.2 mass parts with respect to 100 mass parts polyvinyl acetal particles, and good especially is 0.03～0.1 mass parts.If in this scope, then can be in the good intermiscibility of keeping with polyvinyl acetal, the bonding force of trim plate.
When being configured as sheet, can implement on the polyvinyl acetal particle among the present invention by known manufacturing process.As concrete manufacturing process, can use to melt extrude shaping, press forming, blow molding, injection molded, calendaring molding, casting method and be configured as flaky method.Especially, preferably melt extrude shaping with biaxial extruder with T mould.
Below, describe being used to implement optimal way of the present invention with reference to accompanying drawing.Also have, following Shuo Ming an embodiment example of example representational embodiment of the present invention only, scope of the present invention should not limited thus.
The present invention at first is to use following sheet manufacturing installation, simultaneously feeding resin and softening agent carry out the manufacture method of the extrusion molding of polyvinyl acetal sheet (following also be called for short " sheet "): described manufacturing installation is to be included in (being the polyvinyl acetal particle among the present invention) supply unit and the screw-type extruder of softening agent supply unit and the sheet manufacturing installation with reeling machine of T mould and grain roller that have material resin in the machine barrel, it is characterized in that, in the described screw-type extruder, to the distance to screw front end be made as S from the material resin supply unit, will be from the material resin supply unit when distance to the softening agent supply unit is made as L, L=0.05～0.3.
Used screw-type extruder (following also be called for short " forcing machine ") can use the single shaft forcing machine and the biaxial extruder of the common extrusion molding that is used for thermoplastic resin among the present invention.As biaxial extruder, the homodromal deep channel type of screw rod, the homodromal shallow ridges type of screw rod, the non-homodromal inclined shaft type of screw rod, the non-homodromal parallel shaft type of screw rod etc. are for example arranged.
It is desirable to outlet configuration toothed gear pump at screw-type extruder.Toothed gear pump generally is the gear portion's rotation in the enclosure that makes to make with shell state almost very close to each other, will be through the mechanism that the recording member resin-enclosed space that is produced by rotation and the extruding of plasticising, kneading are carried.By this, can suppress the variation of the extrusion capacity of material resin, it is even that the thickness of the sheet of gained becomes.The ability of toothed gear pump is suitably selected to get final product according to the discharge-amount of forcing machine.
Fig. 1 and Fig. 2 are the synoptic diagram of position relation of material resin supply unit, softening agent supply unit, the screw rod of the machine barrel (cartridge heater) of the screw-type extruder that uses among the present invention of expression.
Among Fig. 1 and Fig. 2, symbol A represents machine barrel, and symbol B represents the material resin supply unit, and symbol C represents the softening agent supply unit, and symbol D represents screw rod.Will be from material resin supply unit B the distance of the front end P to screw rod D be made as 1, will the distance to softening agent supply unit C be made as L from material resin supply unit B.Fig. 1 is corresponding to the situation of L=0.05, and Fig. 2 is corresponding to the situation of L=0.3.Also have, symbol E represents venting hole described later.
Distance L is made as is meant more than at least 0.05 material resin supply unit B and softening agent supply unit C are provided with independently, material resin and softening agent are conducted to machine barrel A (with reference to Fig. 1) respectively.By this, can prevent while and the material resin that in the existing method of same place base feed resin and softening agent, produces and the aggegation of softening agent.Therefore, the mixing efficiency of interior material resin of machine barrel A and softening agent is improved, can suppress the thermolysis of material resin effectively.
In addition, owing to do not need as in the past, will to be conducted to machine barrel after material resin and the plasticizer particleization more in advance the thermal process that material resin is experienced in the time of therefore can removing granulating from yet.
Here, under the situation of L less than 0.05, material resin and softening agent aggegation and mixing efficiency variation near the supply unit of forcing machine, material resin is thermolysis partly.On the other hand, L surpasses under 0.3 the situation, because the time that material resin is mediated under the state of plasticizer-containing not is elongated, so still become material resin pyrolysated major cause.
Therefore,, can suppress the thermolysis of material resin effectively, prevent the painted of sheet by L being set in 0.05～0.3 the scope.The setting range of L better is 0.05～0.2, is more preferably 0.08～0.12.By this, can further improve the transparency of sheet.
Fig. 3 and Fig. 4 are the synoptic diagram of the temperature-controlled process in the machine barrel of the screw-type extruder that is used for illustrating that the present invention uses.
Machine barrel A has the first delivery section A in material resin supply unit B side 1, have the second delivery section A in the front end P of screw rod D side 3, at the first delivery section A 1With the second delivery section A 3Between have compression fusing department A 2In addition, at the second delivery section A 3On be connected with not shown T mould.
The first delivery section A 1Be to make material resin and softening agent blended simultaneously, they are transferred to compression fusing department A 2Part.Compression fusing department A 2It is part with material resin plasticising, kneading.Material resin through mediating is again via the second delivery section A 3Be transferred to the T mould, be extruded, be processed into sheet from the outlet of the resin of T mould.
By with the first delivery section A 1Be made as S/L=1.25～10 apart from S, can avoid material resin experience over-drastic thermal process.During S/L less than 1.0, material resin with under the softening agent blended state be not heated, and causes its experience over-drastic thermal process.In addition, S/L surpasses at 10 o'clock, does not have enough compression fusing department A 2With the second delivery section A 3, the kneading deficiency of material can't obtain uniform sheet.Fig. 3 is corresponding to the situation of S/L=1.25, and Fig. 4 is corresponding to the situation of S/L=10.
The temperature of the material resin in this each position is set by following enforcement, can further reduce the thermal process of material resin experience.
That is the first delivery section A, 1Design temperature be made as the temperature higher 0～110 ℃ than the second-order transition temperature of material resin, better be the temperature higher 10～90 ℃ than second-order transition temperature, be more preferably the temperature higher 20～60 ℃ than second-order transition temperature.Compression fusing department A 2With the second delivery section A 3Design temperature be made as the temperature higher 60～150 ℃ than the second-order transition temperature of material resin, better be the temperature higher 80～140 ℃ than second-order transition temperature, be more preferably the temperature higher 90～130 ℃ than second-order transition temperature.In addition, the design temperature of T mould is made as the temperature higher 70～160 ℃ than the second-order transition temperature of material resin, better is the temperature higher 80～150 ℃ than second-order transition temperature, is more preferably the temperature higher 90～140 ℃ than second-order transition temperature.
Set by the temperature of carrying out as above, can make the temperature of the material resin of T mould outlet is the temperature higher 70～160 ℃ than second-order transition temperature.
Hopper is the structure that is used to lay in material resin and softening agent.The hopper of the screw-type extruder that uses among the present invention better is keep inside airtight.In addition, in order to prevent the oxidation of material resin, better be to have the nitrogen entrance hole.The nitrogen that imports in the hopper further is conducted in the machine barrel, to carrying out nitrogen replacement in hopper and the machine barrel, is discharged from from the venting hole (the symbol E Fig. 1～4) of being located at machine barrel described later.
Venting hole E is for material resin and the contained unwanted volatile components such as moisture of softening agent being discharged to outside the forcing machine, the quality of sheet being improved and the hole of setting.It is desirable to venting hole especially and be located at the second above-mentioned delivery section A 3(with reference to Fig. 3 and Fig. 4).By this, can be to carrying out nitrogen replacement in hopper and the machine barrel in a big way.
On venting hole E, connect not shown various vacuum pumps, attract and volatilize and slough.As vacuum pump, can use used pump usually, water seal type vacuum pump, oil seal type rotary vacuum pump, mechanical booster etc. are for example arranged.If the vacuum tightness when attracting with vacuum pump is located in the scope of 30～500torr, unwanted volatile components such as sloughing moisture then can volatilize under the situation that softening agent itself is not attracted.
Here, import volume about nitrogen, if the feed rate with respect to the material resin of every 100kg/h is supplied with nitrogen continuously with the feed rate of 0.1～600L/h in hopper and machine barrel, then can reduce oxygen partial pressure efficiently, can prevent the oxygenolysis of material resin.Also have, the feed rate of nitrogen better is that the feed rate with respect to the material resin of every 100kg/h is 50～500L/h, is more preferably 200～400L/h.
Material resin can be undertaken by common quantitative feed device etc. to the supply of screw-type extruder, is not particularly limited.For example, have rotary disc feeder, dull and stereotyped feed appliance, pendant thunder (ペ one レ) feed appliance, belt feeder, chain type feed appliance, vibration feeder, shake feed appliance, helical screw feeder etc.
Softening agent can use the pump of common various patterns to the supply of machine barrel, is not particularly limited.For example, reciprocation pump, rotor pump, propeller pump, impeller pump etc. are arranged.
About the addition of softening agent, better be to supply with continuously with the speed of 20～50kg/h with respect to the material resin of every 100kg/h.By making it in this scope, can when keeping melt-shaping, make cementability, toughness reach optimum regime as sheet.The addition of softening agent is more preferably and is made as 30～40kg/h.
The relation to the feed rate sum Q of forcing machine and the rotational speed N s of the screw rod of representing with r.p.m. of material resin of representing with kg/h and softening agent it is desirable in 0.2≤Q/Ns≤0.5, better be in the scope of 0.3≤Q/Ns≤0.5.If in this scope, then material resin and softening agent are fully mediated, and the thermolysis of material resin is inhibited.
Here, Q/Ns is the value of the kneading state of the material resin in the expression forcing machine, and numerical value is more little, and the kneading of expression material resin is abundant more.Q/Ns mediated and becomes insufficient greater than 5 o'clock, and the intermediate coat of gained becomes inhomogeneous.In addition, during Q/Ns less than 0.2, because over-drastic is mediated, thermolysis may take place in material resin.
The thickness of polyvinyl acetal sheet of the present invention better is 0.2～1.5mm, and good especially is 0.3～1mm.Purpose such as these sheets can improve for intensity, sound insulation, thermal insulation, opacifying property, decoration and make preferred polylith more than 2 stacked and duplexer use.Make under the stacked situation of sheet, not only can the identical sheet of stacked composition, can make also that to form different sheets stacked.
As one of problem all the time in the sheet manufacturing, exist in the mutual bonding and incorporate problem of contact surface of sheet when preserving under the state that coils into web-like.
As the method that addresses this problem, the known method that forms embossing on the sheet surface.This embossing also becomes the disengaging path of bubble when making sheet be adhered to glass surface, therefore do not have the remaining laminated glass of bubble also useful for obtaining.
By carrying out embossing processing, can prevent to make the inter-adhesive of sheet when batching behind the film.In addition, when sheet is used as the laminated glass-use intermediate coat, has and drive the effect that residues in the unwanted air between glass and the sheet out of.The degree of depth of embossing and shape use present known pattern to get final product.
The formation method of embossing has grain roller method, stack method, special-shaped extrusion molding, mechanical etching method etc., and what equipment cost was low and efficient is high is the grain roller methods.
In the grain roller method, in the time of will cooling off from the resin that the T mould of forcing machine is extruded in the form of sheets, make sheet press on the surface of grain roller, form embossing on the sheet surface.At this moment, can will once cool off and resin heat once more, utilize the processing of grain roller.
Grain roller are formed with the jog of a large amount of different sizes or cancellate ditch portion etc. on its surface.
The resin of extruding in the form of sheets from the T mould of forcing machine has visco-elasticity, and when therefore being crimped on grain roller, resin may fully be pressed into to the depths of the recess or the ditch of grain roller, can't form required embossing shape.
In addition, utilize grain roller to handle after, when grain roller were decontroled, formed embossing also may can't obtain required embossing shape owing to the visco-elasticity of resin is restored with resin.
In order to address this problem, and embossing the formations method that can evenly process good, the method below the inventor has proposed as processing efficiency.
That is the manufacture method of following polyvinyl acetal sheet: make between 2 grain roller of the configured in parallel that the resin that is extruded in the form of sheets from the T mould represents with following general formula by diameter and surfaceness and carry out surface treatment.
r 1/ r 2＞0.3 and 3.0＞Rz 1/ Rz 2＞1.2
In the formula, r 1The diameter of representing first grain roller, r 2The diameter of representing second grain roller, Rz 1The surfaceness Rz that represents first grain roller, Rz 2The surfaceness Rz that represents second grain roller.
Here, r 1/ r 2Be the value of setting for embossing is transferred to resin accurately, r 1/ r 2＞0.3.That is,, can prolong the time that the resin that is extruded in the form of sheets from the T mould contacts with grain roller, therefore resin can be pressed into fully to the depths of the recess or the ditch of grain roller by setting this value bigger.
In addition, Rz 1/ Rz 2Be the value of setting for the transfer printing state of adjusting embossing, 3.0＞Rz 1/ Rz 2＞1.2.That is,, embossing can be needed on equably the pros and cons of sheet by being set in this scope.
The temperature of first grain roller and second grain roller is set and is respectively 5～15 ℃, 10～20 ℃.By two grain roller are set in this temperature range, the resin that is extruded from the T mould can not adhere to grain roller, and is good from the transferring rate of the embossed pattern of grain roller yet.
The speed of rotation of first grain roller and second grain roller changes according to the target thickness of sheet respectively, is made as 0.5～2.0r.p.m. usually, it is desirable to be provided for the residence time of embossed pattern transfer printing.
Also have, grain roller not only can use the roller of metal, also can use the surface to have concavo-convex rubber.If material adopts rubber, then, therefore can further prolong the time that the resin that is extruded in the form of sheets from the T mould contacts with grain roller because the grain roller surface may be out of shape.
Even the polyvinyl acetal sheet that the shaping of polyvinyl acetal particle is got of the present invention is made 2 above eclipsed duplexers, also very useful as the laminated glass-use intermediate coat, this intermediate coat can be used for the manufacturing of safe laminated glass.
Embodiment
Below, the present invention will be described in more detail to exemplify embodiment, but the present invention should not be construed as and only limits to these embodiment.
(embodiment 1)
The manufacturing of polyvinyl acetal particle
In the dissolving tank of the 3L that has stirrer, drop into the polyvinyl alcohol of 900g pure water and 100g mean polymerisation degree 1700,98 moles of % of saponification deg, heat and obtain polyvinyl alcohol water solution.
Prepare the bottom and have the cylinder glass system closed reactor that three supplying openings, tops have the volume 200ml of a relief outlet, will be full of pure water in this reactor, when stirring, internal temperature is remained on 40 ℃ with the anchor oar.
When under 40 ℃ internal temperature, continuing to adopt the anchor oar to stir, prepare the polyvinyl alcohol water solution of 10 quality % and as 35 quality % hydrochloric acid and butyraldehyde of acid catalyst, import reactor from reactor lower part, the feed speed of polyvinyl alcohol water solution is 60g/h, the feed speed of hydrochloric acid is 5.1g/h, the feed speed of butyraldehyde is 3.6g/h, carries out acetalation.
After the acetalizing degree of the polyvinyl acetal that generates reaches 13 quality %, when importing polyvinyl alcohol water solution, hydrochloric acid and butyraldehyde, discharge reaction solution from the top of reactor from reactor lower part.Collection is from the liquid effluent of closed reactor and measure, and the acetalizing degree of reactor outlet is 40 quality %.The stirring of cylinder glass system closed reactor is during reaction kept all the time and stirred power is 0.8kw/m 3In time, react.
The reactant of discharging is delivered to the ripening tank (feeding amount 1L) of the 2L of other preparation, in ripening tank, add 60 mass parts, 35 quality % hydrochloric acid after, at 60 ℃ of slaking reactions that carry out 4 hours.
Add aqueous sodium hydroxide solution in the reactant after slaking, pH is adjusted to 7.5, acetalation is stopped.After reactant after the neutralization is cooled to normal temperature, filter, use again, obtain the polyvinyl acetal particle with respect to the distilled water washing of 20 times of amounts of polymkeric substance and dry by centrifuge separator.
The peak value of the size distribution of the polyvinyl acetal particle that obtains is 0.25～0.5mm, and its acetalizing degree is 79.8 quality %, and void content is 75%.Also have, the void content of polyvinyl acetal particle uses the (Island Jin System of Shimadzu Scisakusho Ltd to do society of institute) the automatic void content meter of system: Autopore IV9520 is by the mensuration piezometry of mercury penetration method with 0.003MPa～34.5MPa, and the result is 75%.The contact angle of mercury that is used for the mensuration of void content is 140 °, and surface tension is 485 dyne/cm, and density is 13.53g/ml.
(manufacturing of polyvinyl acetal sheet)
With respect to the polyvinyl acetal particle of 100 mass parts gained, add of Triethyleneglycol di 2 ethylhexanoate and the mixing of 35 mass parts as softening agent.The mixture of gained is fully mediated with two rollers that are heated to 85 ℃.With the sheet-like formed thing of gained by the press heating and pressurizing that limits with spacer to pressure 20kg/cm 2, 140 ℃ of temperature, obtain the sheet of thick 0.76mm.
(manufacturing of laminated glass)
The polyvinyl acetal sheet of gained is between the foursquare transparent float glass plate that sandwich-like is sandwiched in 2 length of side 300mm, thick 2mm, with the pre-crimping of roll-in method.Then, in 140 ℃ autoclave with 12kg/cm 2Pressure crimping 30 minutes, obtain laminated glass.
(anti-perfoliate mensuration)
The anti-perfoliate mensuration of sheet is following carries out: according to JIS R 3212, the steel ball that makes quality 2260 ± 20g, the about 82mm of diameter falls to the central part of sample at 25 ℃ with 55 ℃ of laminated glass sample tops of having preserved the about 300 * 300mm more than 4 hours with different height.Test is carried out repeatedly, and the maximum height the when steel ball of obtaining test over half does not run through should be highly as the anti-performance that runs through.
(melt extruding performance evaluation)
To in the polyvinyl acetal particle that obtains by the present invention, mediate mixture that 35 mass parts softening agent Triethyleneglycol di 2 ethylhexanoates get and drop into continuously and link the biaxial extruder that the T mould is arranged, in table 1, extrude in the form of sheets under the T mould design temperature of record.
Whether the sheet that obtains thus by visual inspection has not melts, and measures near the temperature of the mixture the forcing machine Inner Front End, the just sheet temperature when the T mould is discharged.
(embodiment 2)
Among the embodiment 1, except the mixture (acetaldehyde/butyraldehyde=50/50 mass ratio) of supplying with acetaldehyde and butyraldehyde with the feed speed of 3.3g/h replaces butyraldehyde, react similarly to Example 1, obtain the polyvinyl acetal particle and estimate.The peak value of the size distribution of the polyvinyl acetal particle that obtains is 0.15～0.25mm, and acetalizing degree is 83.2 quality %, and void content is 82%.
(embodiment 3)
Except the stirring power with cylinder glass system closed reactor is made as 0.5kw/m 3In addition, react similarly to Example 2, obtain the polyvinyl acetal particle and estimate.The peak value of the size distribution of the polyvinyl acetal particle that obtains is 0.15～0.25mm, and acetalizing degree is 83.1 quality %, and void content is 70%.
(embodiment 4)
Except the stirring power with cylinder glass system closed reactor is made as 1.2kw/m 3In addition, react similarly to Example 2, obtain the polyvinyl acetal particle and estimate.The peak value of the size distribution of the polyvinyl acetal particle that obtains is 0.15～0.25mm, and acetalizing degree is 82.9 quality %, and void content is 78%.
(embodiment 5)
Except temperature of reaction is made as 50 ℃ all the time, react similarly to Example 2, obtain the polyvinyl acetal particle and estimate.The peak value of the size distribution of the polyvinyl acetal particle that obtains is 0.15～0.25mm, and acetalizing degree is 83.5 quality %, and void content is 77%.
(embodiment 6)
Except the temperature with cylinder glass system closed reactor is made as 30 ℃, the temperature of ripening tank is made as beyond 60 ℃, reacts similarly to Example 2, obtains the polyvinyl acetal particle and estimates.The peak value of the size distribution of the polyvinyl acetal particle that obtains is 0.15～0.25mm, and acetalizing degree is 82.7 quality %, and void content is 75%.
(embodiment 7)
Among the embodiment 2, except the ratio with the mixture of acetaldehyde and butyraldehyde is made as acetaldehyde/butyraldehyde=70/30 mass ratio, react similarly to Example 2, obtain the polyvinyl acetal particle and estimate.The peak value of the size distribution of the polyvinyl acetal particle that obtains is 0.15～0.25mm, and acetalizing degree is 81.7 quality %, and void content is 80%.
(embodiment 8)
Among the embodiment 2, except the ratio with the mixture of acetaldehyde and butyraldehyde is made as acetaldehyde/butyraldehyde=30/70 mass ratio, react similarly to Example 2, obtain the polyvinyl acetal particle and estimate.The peak value of the size distribution of the polyvinyl acetal particle that obtains is 0.15～0.25mm, and acetalizing degree is 82.0 quality %, and void content is 73%.
(embodiment 9)
Among the embodiment 2, except the polyvinyl alcohol that uses mean polymerisation degree 2000,98.5 moles of % of saponification deg, react similarly to Example 2, obtain the polyvinyl acetal particle and estimate.The peak value of the size distribution of the polyvinyl acetal particle that obtains is 0.15～0.25mm, and acetalizing degree is 83.0 quality %, and void content is 81%.
(embodiment 10)
Among the embodiment 1, the softening agent addition when sheet is made and when melt extruding performance evaluation is made as the 40 quality %, makes sheet similarly to Example 1, implementation evaluation.
The rerum natura of the polyvinyl acetal particle of creating conditions, obtaining of the polyvinyl acetal particle of embodiment 1～10 and the performance evaluation result of sheet etc. gather and are shown in table 1.
(embodiment 11)
When making laminated glass, as being sandwiched in 2 sheets between sheet glass, use the sheet that obtains among the sheet that will obtain among the embodiment 1 and the embodiment 2 overlapping and duplexer beyond, operate similarly to Example 1, make laminated glass.
(embodiment 12)
When making laminated glass, as be sandwiched in 2 sheets between sheet glass use the sheet that obtains among the sheet that will obtain among the embodiment 2 and the embodiment 6 overlapping and duplexer beyond, operate similarly to Example 1, make laminated glass.
(embodiment 13)
When making laminated glass, as be sandwiched in 2 sheets between sheet glass use the sheet that obtains among the sheet that will obtain among the embodiment 1 and the embodiment 10 overlapping and duplexer beyond, operate similarly to Example 1, make laminated glass.
(embodiment 14)
When making laminated glass, be sandwiched in 2 sheets between sheet glass and use with the sheet that obtains among the embodiment 2 and clamp the sheet that obtains the embodiment 1 from both sides and beyond 3 layers the duplexer that forms, operate similarly to Example 1, make laminated glass.
(embodiment 15)
When making laminated glass, as being sandwiched in 2 sheets between sheet glass, the both sides of using the sheet that obtains with the sheet that obtains among the embodiment 1 from embodiment 2 are clamped and beyond 3 layers the duplexer forming, are operated similarly to Example 1, make laminated glass.
The anti-evaluation that runs through performance of embodiment 11～15 gathers and is shown in table 2.
(comparative example 1)
Except temperature of reaction is made as 70 ℃ all the time, react similarly to Example 1, obtain the polyvinyl acetal particle and estimate.The peak value of the size distribution of the polyvinyl acetal particle that obtains is 0.25～0.5mm, and acetalizing degree is 80.5 quality %, and void content is 55%.
(comparative example 2)
Except temperature of reaction is made as 10 ℃ all the time, react similarly to Example 1, obtain the polyvinyl acetal particle and estimate.The peak value of the size distribution of the polyvinyl acetal particle that obtains is 0.25～0.5mm, and acetalizing degree is 70.0 quality %, and void content is 67%.
(comparative example 3)
Be made as 0.3kw/m except stirring power 3In addition, react similarly to Example 2, obtain the polyvinyl acetal particle and estimate.The peak value of the size distribution of the polyvinyl acetal particle that obtains is 0.15～0.25mm, and acetalizing degree is 83.0 quality %, and void content is 58%.
The rerum natura of comparative example 1～3, performance evaluation result etc. gather and are shown in table 1.
Table 1
(table 1 is continuous)
* 1:A acetaldehyde, the B butyraldehyde
* 2: not fusant is arranged in the sheet
Table 2
Figure A20078003900000262
(embodiment 21)
(system film test equipment)
Embodiment is undertaken by following system film test equipment.
(1) screw-type extruder: system biaxial extruder (screw rod φ 48mm, L/D=45, carrying raw material resin supplying opening, softening agent supplying opening, venting hole) (East Zhi Machine tool society of Toshiba Machinery Co., Ltd.).
(2) from the material resin supply unit of forcing machine, when the distance of near screw front end is made as S, to the distance L of softening agent supply unit: 0.15.
(3) material resin hopper: the 200L jar, helical screw feeder is established in a jar bottom, and nitrogen is enclosed closed structure.
(4) softening agent jar: 200L jar.
(5) softening agent supply pump: triplex plunger pump (science and technology Co., Ltd. of Fuji (Off ジ テ Network ノ society) system).
(6) vacuum pump: slough with venting hole in the volatilization of forcing machine and to establish oil seal type rotary vacuum pump (DaHuang Machine Industry Co., Ltd ( イ コ ウ Machine tool society) system).Vacuum tightness is made as 300torr.
(7) toothed gear pump: establish toothed gear pump (ability 120L/h) at outlet of extruder.
(8) T mould: wide 1100mm.
(9) grain roller (reeling machine): first roller, the wide 1200mm of roller, diameter r 1=600mm, surfaceness Rz 1=45 μ m; Second roller, the wide 1200mm of roller, diameter r 2=450mm, surfaceness Rz 2=30 μ m; r 1/ r 2=1.3, Rz 1/ Rz 2=1.5.
(film forming condition)
In the material resin,, use the polyvinyl butyral acetal (mean polymerisation degree 1700, void content 78%, 73 ℃ of second-order transition temperatures, acetalizing degree 79.8 quality %) that gets with butyraldehyde (representing with B in the table 1) acetalation as polyvinyl acetal.
In addition, softening agent uses Triethyleneglycol di 2 ethylhexanoate.With the raw material hopper with nitrogen replacement after, add polyvinyl butyral acetal, it is airtight to close lid.When supplying with nitrogen, make film.The condition of system film is as described below.
(1) material resin is to the supply of screw-type extruder: 50kg/h.
(2) supply of nitrogen in material resin hopper and machine barrel: 120L/h (with the speed base feed resin of 100kg/h time be 240L/h).Supply with continuously in the system film always.
(3) supply of softening agent: 17kg/h (with the speed base feed resin of 100kg/h time be 34kg/h).
(4) rotating speed of extruder screw (Ns): 150r.p.m..
Feed rate (kg/h) the sum Q (kg/h) of feed rate of material resin (kg/h) and softening agent/Ns=(50+17)/150=0.45.
(5) machine barrel design temperature: 180 ℃ (material resin supply unit and softening agent supply unit are equivalent to " the first delivery section A illustrated in fig. 3 for 140 ℃ of material resin supply units and softening agent supply unit 1"), kneading portion to outlet of extruder (is equivalent to " compression fusing department A equally certainly 2" and " the second delivery section A 3") 200 ℃.
(6) T mould design temperature: 200 ℃.
By carrying out above setting, the resin temperature of outlet of extruder is 210 ℃, and the resin temperature of T mould outlet is 210 ℃ (second-order transition temperatures (73 ℃)+137 ℃).
(7) gap of T mould die orifice (the opening thickness of T mould): 0.95mm.
Also have, the thickness of the sheet after batching is 0.76mm (thickness=1.25 of the opening thickness/sheet of T mould).
(8) the coiling speed 1.4m/ of reeling machine minute.
(evaluation of the yellow chromaticity of sheet)
Measure the yellow chromaticity of sheet by transmission method according to JIS K 7105.
(the surfaceness evaluation of sheet)
By surfaceness meter (the accurate society in Tokyo Precision Co., Ltd (East capital) system SURFCOM 1500D) the mensuration surfaceness.In the mensuration, the face that will contact with reeling machine first roller is as the front, and the face that contacts with second roller is as reverse side.
(evaluation of the adhesive of sheet)
When being rolled into, sheet is difficult for taking place the evaluation of the degree of the bonding adhesion that causes of oneself, 2 sheet pros and cons that will be cut into 150mm * 50mm are overlapping, carry the load of 2kg thereon, 20 ℃ place 24 hours after, by 180 ° of peeling forces of 100mm/ minute of stretching test machine determination speed.This value is big more, and then intermembranous bonding force is big more.
(manufacturing of laminated glass)
The sheet of gained is sandwiched between the float glass of 2 thick 3mm, with the pre-crimping of roll-in method.Then, in 140 ℃ autoclave with 12kg/cm 2Pressure crimping 30 minutes, obtain transparent laminated glass.
(evaluation of the yellow chromaticity of laminated glass)
Measure the yellow chromaticity of the laminated glass of making by transmission method according to JIS K 7105.
(evaluation that the bubble of laminated glass is residual)
As the evaluation of the bubble residual quantity of the laminated glass of making by sheet, prepare the laminated glass of 30 300mm * 300mm, after 2 hours, measure the piece number of the laminated glass that produces macroscopic bubble 120 ℃ of heating.Evaluation result is represented with the ratio that foaming piece number is equivalent to the sample blocks number.
(anti-perfoliate mensuration)
The anti-perfoliate mensuration of laminated glass is following carries out: according to JIS R 3212, the steel ball that makes quality 2260 ± 20g, the about 82mm of diameter falls to the central part of sample at 25 ℃ with 55 ℃ of laminated glass sample tops of having preserved the about 300 * 300mm more than 4 hours with different height.Test repeats in the height of fall that constantly increases steel ball, obtains the maximum height that 50% the number of times that is equivalent to test number (TN) in the test of sustained height does not run through, with it as the anti-performance that runs through.
(embodiment 22)
Except the material resin supply unit from forcing machine, when the distance of near screw front end was made as S, the distance L of near softening agent supply unit was made as beyond 0.05, made sheet and estimated by method similarly to Example 21.
(embodiment 23)
Except the material resin supply unit from forcing machine, when the distance of near screw front end was made as S, the distance L of near softening agent supply unit was made as beyond 0.08, made sheet and estimated by method similarly to Example 21.
(embodiment 24)
Except the material resin supply unit from forcing machine, when the distance of near screw front end was made as S, the distance L of near softening agent supply unit was made as beyond 0.3, made sheet and estimated by method similarly to Example 2.
(embodiment 25)
Except by will be from forcing machine kneading portion the design temperature of the machine barrel design temperature to outlet of extruder and T mould be made as 140 ℃, the resin temperature that makes T mould outlet be 143 ℃ (second-order transition temperature+70 ℃) in addition, make sheet and estimate by method similarly to Example 21.
(embodiment 26)
Except by will be from forcing machine kneading portion the design temperature of the machine barrel design temperature to outlet of extruder and T mould be made as 220 ℃, the resin temperature that makes T mould outlet be 230 ℃ (second-order transition temperature+157 ℃) in addition, make sheet and estimate by method similarly to Example 21.
(embodiment 27)
Except by will be from forcing machine kneading portion the design temperature of the machine barrel design temperature to outlet of extruder and T mould be made as 125 ℃, the resin temperature that makes T mould outlet be 130 ℃ (second-order transition temperature+57 ℃) in addition, make sheet and estimate by method similarly to Example 21.
(embodiment 28)
Except by will be from forcing machine kneading portion the design temperature of the machine barrel design temperature to outlet of extruder and T mould be made as 240 ℃, the resin temperature that makes T mould outlet be 250 ℃ (second-order transition temperature+177 ℃) in addition, make sheet and estimate by method similarly to Example 21.
(embodiment 29)
Except behind the nitrogen replacement that carries out the raw material hopper, beyond in sheet is made, importing, make sheet and estimate by method similarly to Example 21 with the speed (supply of the material resin of every 100kg is 0.1L/h) of 0.05L/h.
(embodiment 30)
Except behind the nitrogen replacement that carries out the raw material hopper, beyond in sheet is made, importing, make sheet and estimate by method similarly to Example 21 with the speed (supply of the material resin of every 100kg is 600L/h) of 300L/h.
(embodiment 31)
Except behind the nitrogen replacement that carries out the raw material hopper, beyond in sheet is made, importing, make sheet and estimate by method similarly to Example 21 with the speed (supply of the material resin of every 100kg is 0.08L/h) of 0.04L/h.
(embodiment 32)
Except behind the nitrogen replacement that carries out the raw material hopper, beyond in sheet is made, importing, make sheet and estimate by method similarly to Example 21 with the speed (supply of the material resin of every 100kg is 800L/h) of 400L/h.
(embodiment 33)
Except softening agent is made as 10kg/h (with the speed base feed resin of 100kg/h time be 20kg/h) imports to the feed speed of forcing machine, makes sheet and estimate by method similarly to Example 21.
(embodiment 34)
Except softening agent is made as 25kg/h (with the speed base feed resin of 100kg/h time be 50kg/h) imports to the feed speed of forcing machine, makes sheet and estimate by method similarly to Example 21.
(embodiment 35)
Except softening agent is made as 7kg/h (with the speed base feed resin of 100kg/h time be 14kg/h) imports to the feed speed of forcing machine, makes sheet and estimate by method similarly to Example 21.
(embodiment 36)
Except softening agent is made as 27.5kg/h (with the speed base feed resin of 100kg/h time be 55kg/h) imports to the feed speed of forcing machine, makes sheet and estimate by method similarly to Example 21.
(embodiment 37)
Except will being made as 0.2, making sheet and estimate by method similarly to Example 21 to feed rate (kg/h) the sum Q (kg/h) of the feed rate (kg/h) of the material resin of forcing machine and softening agent and the Q/Ns that concerns of screw speed Ns (r.p.m.).
(embodiment 38)
Except will being made as 0.5, making sheet and estimate by method similarly to Example 21 to feed rate (kg/h) the sum Q (kg/h) of the feed rate (kg/h) of the material resin of forcing machine and softening agent and the Q/Ns that concerns of screw speed Ns (r.p.m.).
(embodiment 39)
Except will being made as 0.15, making sheet and estimate by method similarly to Example 21 to feed rate (kg/h) the sum Q (kg/h) of the feed rate (kg/h) of the material resin of forcing machine and softening agent and the Q/Ns that concerns of screw speed Ns (r.p.m.).
(embodiment 40)
Except will being made as 0.6, making sheet and estimate by method similarly to Example 21 to feed rate (kg/h) the sum Q (kg/h) of the feed rate (kg/h) of the material resin of forcing machine and softening agent and the Q/Ns that concerns of screw speed Ns (r.p.m.).
The evaluation result of embodiment 21～40 gathers and is shown in table 3.
(embodiment 41)
Except material resin adopts the vinyl-vinyl-acetic ester multipolymer, softening agent adopts beyond phthalic acid two-2-ethylhexyl, makes sheet and estimates by method similarly to Example 21.
(embodiment 42)
Except polyvinyl acetal as material resin, use with the quality of acetaldehyde/butyraldehyde (representing with A/B in the table 4)=50/50 than acetalation and resin (mean polymerisation degree 1700, void content 80%, 93 ℃ of second-order transition temperatures, acetalizing degree 83.2 quality %) in addition, make sheet by method similarly to Example 21 and estimate.
(embodiment 43)
Except polyvinyl acetal as material resin, use with the quality of acetaldehyde/butyraldehyde (representing with A/B in the table 4)=70/30 than acetalation and resin (mean polymerisation degree 1700, void content 79%, 97 ℃ of second-order transition temperatures, acetalizing degree 83.5 quality %) in addition, make sheet by method similarly to Example 21 and estimate.
(embodiment 44)
Except polyvinyl acetal as material resin, use with the quality of acetaldehyde/butyraldehyde (representing with A/B in the table 4)=30/70 than acetalation and resin (mean polymerisation degree 1700, void content 78%, 97 ℃ of second-order transition temperatures, acetalizing degree 83.5 quality %) in addition, make sheet by method similarly to Example 21 and estimate.
(embodiment 45)
Except the acetalizing degree of the polyvinyl butyral acetal that makes material resin is 70 quality %, makes sheet and estimate by method similarly to Example 21.
(embodiment 46)
Except the acetalizing degree of the polyvinyl butyral acetal that makes material resin is 86 quality %, makes sheet and estimate by method similarly to Example 21.
(embodiment 47)
Except the void content of the polyvinyl butyral acetal that makes material resin is 58 quality %, makes sheet and estimate by method similarly to Example 21.
(embodiment 48)
Except the void content of the polyvinyl butyral acetal that makes material resin is 88 quality %, makes sheet and estimate by method similarly to Example 21.
(embodiment 49)
Except softening agent uses triglycol-2 Ethylbutanoic acid ester, make sheet and estimate by method similarly to Example 21.
(embodiment 50)
Except the gap (the opening thickness of T mould) that makes T mould die orifice for the 1.30mm (sheet thickness 1.7 times), make sheet and estimate by method similarly to Example 21.
(embodiment 51)
Except first roller of grain roller is made as diameter r 1=150mm, second roller is made as diameter r 2=600mm (r 1/ r 2=0.25) in addition, makes sheet and estimate by method similarly to Example 21.
(embodiment 52)
Except first roller of grain roller is made as surfaceness Rz 1=30 μ m, second roller is made as surfaceness Rz 2=30 μ m (Rz 1/ Rz 2=1.0) in addition, make sheet and estimate by method similarly to Example 21.
(embodiment 53)
Except first roller of grain roller is made as surfaceness Rz 1=57 μ m, second roller is made as surfaceness Rz 2=18 μ m (Rz 1/ Rz 2=3.2) in addition, make sheet and estimate by method similarly to Example 21.
(comparative example 21)
Except the material resin supply unit from forcing machine, when the distance of near screw front end was made as S, the distance L of near softening agent supply unit was made as beyond 0.03, made sheet and estimated by method similarly to Example 21.
In the present embodiment, near the material resin supply unit of forcing machine, produce the arch formation of material resin, can't extrudate piece.
(comparative example 22)
Except the material resin supply unit from forcing machine, when the distance of near screw front end was made as S, the distance L of near softening agent supply unit was made as beyond 0.4, made sheet and estimated by method similarly to Example 21.
The evaluation result of embodiment 41～53, comparative example 21 and comparative example 22 gathers and is shown in table 4.
Figure A20078003900000351
As shown in the above description, under the situation of distance L less than 0.05 from the material resin supply unit of screw-type extruder, near the material resin supply unit, may produce the arch formation (comparative example 21) of material resin to the softening agent supply unit.In addition, L surpasses under 0.3 the situation, and the degree of staining of sheet (yellow chromaticity) increases (comparative example 22).
Relative with it, under the situation of L in 0.05～0.3 numerical range, can obtain the sheet (embodiment 21～24) that degree of staining is low, the transparency is high.
In addition, the adhesive of the sheet that obtains among the embodiment 21～24 is also low.In addition, the painted and foaming of the less generation of the laminated glass that uses these sheets to make, anti-penetrability good (embodiment 21～24).
Among the embodiment 25～28, the material resin temperature of the T mould of forcing machine outlet is studied.
Among embodiment 29～32 and the embodiment 33～36, the feed rate of nitrogen and softening agent is studied, among the embodiment 37～40, screw speed is studied.
Among the embodiment 41～48, material resin and void content thereof and acetalizing degree are studied, among the embodiment 49, softening agent is studied.
Among the embodiment 50, the opening thickness of T mould is studied, among the embodiment 51～53, the diameter and the surfaceness of grain roller are studied.
Above studies show that, by with these setting values in specific scope, can make degree of staining low, all have required embossing, sheet that adhesive is low equably at pros and cons.And, be presented at and also can suppress generation painted and foaming in the manufacturing of laminated glass, anti-penetrability is improved.
The possibility of utilizing on the industry
The polyvinyl acetal sheet that obtains by the present invention and the cementability of glass are good, the accent of cementability Lift face is easy, and degree of staining is low, and the transparency is high and at high temperature also have a good anti-performance that runs through, so Intermediate coat as laminated glass is very good. In addition, adopt the polyvinyl alcohol that obtains by the present invention The laminated glass of acetal sheet can perform well in automobile, building or house etc.
Here quote Japanese patent application 2006-287913 number and 2 that filed an application on October 23rd, 2006 Japanese patent application 2007-120466 number specification, the claim of filing an application on May 1st, 007 All the elements of book, accompanying drawing and summary are as the announcement of specification of the present invention.

Claims (16)

1. polyvinyl acetal sheet is characterized in that, acetalizing degree is that 75.0～84.0 quality % and void content are that 60～85% polyvinyl acetal particle is configured as sheet and forms.
2. polyvinyl acetal sheet as claimed in claim 1, it is characterized in that, the polyvinyl acetal particle is following to be obtained: make 100 mass parts polyvinyl alcohol and 40～75 mass parts aldehyde in the presence of an acidic catalyst when 20～60 ℃ temperature is carried out acetalation, polyvinyl alcohol, aldehyde and an acidic catalyst are conducted to reactor carry out acetalation, after the acetalizing degree of the polyvinyl acetal that generates reaches at least 13 quality %, discharge reactant from described reactor, make the reactant that is discharged from carry out slaking reaction.
3. polyvinyl acetal sheet as claimed in claim 2 is characterized in that, reactor is the reactor that has been full of reaction solution in the container.
4. as claim 2 or 3 described polyvinyl acetal sheets, it is characterized in that the stirring power with unit volume 0.5～1.5kw in the reactor stirs.
5. as each the described polyvinyl acetal sheet in the claim 1～4, it is characterized in that aldehyde comprises butyraldehyde at least.
6. as each the described polyvinyl acetal sheet in the claim 1～5, it is characterized in that,, comprise 10～50 mass parts softening agent with respect to 100 mass parts polyvinyl acetals.
7. duplexer is characterized in that, each the described polyvinyl acetal sheet in 2 above claims 1～6 is overlapping and get.
8. the laminated glass-use intermediate coat is characterized in that, adopts each described polyvinyl acetal sheet or duplexer in the claim 1～7.
9. the manufacture method of the described polyvinyl acetal sheet of claim 1 is characterized in that, uses the sheet manufacturing installation, supplies with polyvinyl acetal particle and softening agent and carries out extrusion molding; Described manufacturing installation comprises screw-type extruder with polyvinyl acetal particle supply unit and softening agent supply unit and the reeling machine with T mould and grain roller, and with the distance to screw front end is made as 1 from polyvinyl acetal particle supply unit in the described screw-type extruder, will be from polyvinyl acetal particle supply unit when the distance to the softening agent supply unit is made as L, L=0.05～0.3.
10. the manufacture method of polyvinyl acetal sheet as claimed in claim 9 is characterized in that, with respect to the feed rate of the described polyvinyl acetal particle of every 100kg/h, supplies with described softening agent continuously with the feed rate of 20～50kg/h.
11. manufacture method as claim 9 or 10 described polyvinyl acetal sheets, it is characterized in that, the feed rate of the described polyvinyl acetal particle that will represent with kg/h is made as the Q that represents with kg/h with the feed rate sum of the described softening agent of representing with kg/h, when the rotating speed of the described screw rod that will represent with r.p.m. is made as Ns, 0.2≤Q/Ns≤0.5.
12. the manufacture method as each the described polyvinyl acetal sheet in the claim 9～11 is characterized in that, described softening agent is a Triethyleneglycol di 2 ethylhexanoate.
13. the manufacture method as each the described polyvinyl acetal sheet in the claim 9～12 is characterized in that, the opening thickness of described T mould is 1～1.6 times of thickness of the polyvinyl acetal sheet of manufacturing.
14. manufacture method as each the described polyvinyl acetal sheet in the claim 9～13, it is characterized in that, described grain roller are to have with the diameter of following formula (1) expression and 2 grain roller that are arranged in parallel of surfaceness, make the polyvinyl acetal particle that is extruded from described T mould by carrying out surface treatment between the described grain roller;
r 1/ r 2＞0.3 and 3.0＞Rz 1/ Rz 2＞1.2 (1)
In the formula, r 1The diameter of representing first grain roller, r 2The diameter of representing second grain roller, Rz 1The surfaceness Rz that represents first grain roller, Rz 2The surfaceness Rz that represents second grain roller.
15. the laminated glass-use intermediate coat is characterized in that, adopts the polyvinyl acetal sheet that obtains by each the described manufacture method in the claim 9～14.
16. laminated glass is characterized in that, adopts claim 8 or 15 described laminated glass-use intermediate coats.
CNA2007800390000A 2006-10-23 2007-07-27 Polyvinyl acetal sheet and process for production thereof Pending CN101528819A (en)

Applications Claiming Priority (3)

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JP287913/2006 2006-10-23
JP2006287913 2006-10-23
JP120466/2007 2007-05-01

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101962462A (en) * 2010-10-30 2011-02-02 浙江德斯泰塑胶有限公司 PVB intermediate film with fireproof function
CN107001757A (en) * 2014-12-08 2017-08-01 首诺公司 Poly- (vinyl acetal) resin combination, layer and interlayer with enhanced optical property
CN108527814A (en) * 2017-03-03 2018-09-14 住友化学株式会社 The manufacturing method of kneading device and mixture
CN111499780A (en) * 2020-05-26 2020-08-07 河南省科学院化学研究所有限公司 Synthetic method of polyvinyl butyral resin
CN113667253A (en) * 2021-09-13 2021-11-19 深圳市智远隆材料科技有限公司 Hardness-controllable low-temperature soluble bridge plug sealing element and preparation method thereof
CN114805862A (en) * 2022-05-18 2022-07-29 广东工业大学 Recyclable temporary corneal prosthesis or contact lens based on modified PVA derivative hydrogel material

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101962462A (en) * 2010-10-30 2011-02-02 浙江德斯泰塑胶有限公司 PVB intermediate film with fireproof function
CN107001757A (en) * 2014-12-08 2017-08-01 首诺公司 Poly- (vinyl acetal) resin combination, layer and interlayer with enhanced optical property
CN108527814A (en) * 2017-03-03 2018-09-14 住友化学株式会社 The manufacturing method of kneading device and mixture
CN111499780A (en) * 2020-05-26 2020-08-07 河南省科学院化学研究所有限公司 Synthetic method of polyvinyl butyral resin
CN111499780B (en) * 2020-05-26 2023-01-24 河南省科学院化学研究所有限公司 Synthetic method of polyvinyl butyral resin
CN113667253A (en) * 2021-09-13 2021-11-19 深圳市智远隆材料科技有限公司 Hardness-controllable low-temperature soluble bridge plug sealing element and preparation method thereof
CN113667253B (en) * 2021-09-13 2023-06-16 深圳市智远隆材料科技有限公司 Hardness-controllable low-temperature soluble bridge plug sealing element and preparation method thereof
CN114805862A (en) * 2022-05-18 2022-07-29 广东工业大学 Recyclable temporary corneal prosthesis or contact lens based on modified PVA derivative hydrogel material

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