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WO1992000349A1 - Polybutyral de vinyl plastifie et sa feuille formee - Google Patents

Polybutyral de vinyl plastifie et sa feuille formee Download PDF

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Publication number
WO1992000349A1
WO1992000349A1 PCT/US1991/004402 US9104402W WO9200349A1 WO 1992000349 A1 WO1992000349 A1 WO 1992000349A1 US 9104402 W US9104402 W US 9104402W WO 9200349 A1 WO9200349 A1 WO 9200349A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
mixture
polyvinyl butyral
butyral resin
sheet
Prior art date
Application number
PCT/US1991/004402
Other languages
English (en)
Inventor
Ildefonso Luis Gomez
Roland Joseph Tetreault
Original Assignee
Monsanto Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Monsanto Company filed Critical Monsanto Company
Publication of WO1992000349A1 publication Critical patent/WO1992000349A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10761—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing vinyl acetal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10559—Shape of the cross-section
    • B32B17/10577—Surface roughness
    • B32B17/10596—Surface roughness created by melt fracture
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10605—Type of plasticiser
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols

Definitions

  • This invention relates to plasticized poly- vinyl butyral resin and sheet formed therefrom and more particularly to improving the performance of dioctyl adipate as the plasticizer therein.
  • Polyvinyl butyral resin as sheet for use as an optically transparent, impact-dissipating inter- layer in laminated safety glazings is well known.
  • DOA dioctyl adipate
  • examples 42-45 of U.S. 3,884,865 DOA is an ineffective plasticizer of polyvinyl butyral resin of the type used with glass in laminated glazings.
  • Such resin for use as sheet in safety glazings is composed of polyvinyl alcohol partially condensed with butyral- dehyde so as to contain from 15% to 25%, preferably, 18 to 24% by weight, unreacted hydroxyl groups.
  • This material is commonly called polyvinyl butyral or more exactly "partial polyvinyl butyral", hereinafter sometimes abbreviated as PVB.
  • a principal object of this invention is to improve the effectiveness of DOA as a plasticizer for PVB resin.
  • Another object is to provide an improved DOA plasticizer composition for PVB resin.
  • a method of improving the effectiveness of dioctyl adipate as a plasticizer for partial polyvinyl butyral resin which comprises incorporating into a mixture of dioctyl adipate and the resin, an exudation- reducing amount of a composition of i) one or more monoesters of a glycol and a C l ⁇ to C 2 _ unsaturated fatty acid having a hydroxyl group attached to the acid molecule or ii) castor oil or iii) a mixture of said one or more monoesters and castor oil, the ratio of one or more monoesters to castor oil in the mixture of iii) being between about 1:1 to about 5:1.
  • the major dioctyl adipate component of the plasticizer blend of the invention comprises one or more dioctyl esters of adipic acid.
  • the octyl moiety of the ester can be linear (i.e. n-octyl) or any form of a branched octyl moiety including mixtures of linear and branched octyl moieties. Pure (100%) di(2-ethyl hexyl) adipate is preferred.
  • the major (more than 50 weight %) adipate component of the plasticizer blend of the invention is prepared by esterifying adipic acid and one or more linear or branched octyl alcohols according to syn- thesis procedures well known to those skilled in the art. Depending on alcohols chosen, the resulting product is a pure or mixed adipate. Ethyl hexyl alcohol is preferred which, after esterification, provides pure di(2-ethyl hexyl) adipate. Dioctyl adipate is also available commer ⁇ cially from Akzo; Ashland Chemical Co.; Exxon Chemical Co.; H ⁇ ls-America and Monsanto Co.
  • the minor component of the plasticizer blend of the invention is described in U.S. 4,563,296, Col. 3, lines 11-59. More particularly, such minor component is a composition of: i) one or more mono ⁇ esters of a glycol and a C.,, to C 2Q unsaturated fatty acid having a hydroxyl group attached to the acid molecule or ii) castor oil or iii) a mixture of said one or more monoesters and castor oil.
  • the mixture iii) of components i) and ii) is preferred.
  • Component i) comprises a monoester of a glycol and a c 16 to C 2 unsaturat ⁇ d fatty acid having a hydroxyl group attached to the acid molecule.
  • the preferred monoester is propylene glycol 1,2 mono- ricinoleate.
  • Acids which can be used to form the monoester have 10 to 20 carbon atoms and include, in addition to ricinoleic acid (12-hydroxyoleic acid), other hydroxy-oleic acids with the hydroxyl groups located other than on the "12" carbon atom such as 6-,8-,14-, or 16-hydroxy-oleic acid, 12-hydroxyelaidic acid and acids with the same empirical formula with the hydroxyl located other than on the "12" atom. Included also are the corresponding variations of 12-hydroxy-hexodec-9-enoic acid and 12-hydroxy-eicos- 9-enoic acid.
  • a single acid may provide all the esterifying acid groups but usually a mixture of unsaturated esterifying acids are used provided the esterifying acids together provide at least one unsaturation and one hydroxyl groups per molecule of monoester.
  • Component ii) as castor oil is a triglyceride ester of unsaturated fatty acids. It comprises a mixture of esters of glycerol with the following acids, (the figures in parentheses being the approximate weight % of ester formed from that acid): ricinoleic acid (89.5%), oleic acid (3.0%), linoleic acid (4.2%), and dihydroxy-stearic acid (0.7%).
  • the weight proportion of monoester i) to castor oil ii) should be between about 1:1 to about 5:1. It is preferred that the monoester be the major component of this minor constituent mixture and therefore be present in an amount greater than the castor oil. The most preferred proportion of monoester to castor oil is 2.3:1.
  • the monoesters are commercially available from CasChem Inc., Bayonne, N.J., 07002 under the registered trademark Flexricin. The various grades of each used in the Examples following are identified in the footnotes to Table 1. Castor oil is likewise available from this firm.
  • the exudation-reducing amount of the minor component in the plasticizer blend will vary depending on the particular property of the sheet formed of the formulation is desired to be improved. Based on the total weight of plasticizer blend, the amount of monoester or castor oil or combined monoester/castor oil constituent is always less than the primary DOA component.
  • the preferred weight ratio of the DOA major component to the minor monoester or castor oil or mixed monoester/castor oil component is between about 5:1 to 1.9:1 and preferably about 3:1.
  • a preferred plasticizer composition is about 65-95%, preferably 70-90% DOA and correspondingly 35-5%, preferably 30-10% minor component.
  • the total amount of plasticizer in the formulation to form the interlayer sheet depends on the specific PVB resin and the properties desired in the sheet application. Generally between 15 to 50, preferably 25 to 40 parts total plasticizer per 100 parts of PVB resin (PHR) is used.
  • the PVB resin employed has a weight average molecular weight greater than 100,000, preferably from about 200,000 to 300,000, as measured by size exclusion chromatography using low angle laser light scattering.
  • Such PVB comprises, on a weight basis, 15 to 25%, preferably 18 to 24% hydroxyl groups calculated as polyvinyl alcohol (PVOH); 0 to 10%, preferably 0 to 3% residual ester groups, calculated as polyvinyl ester, e.g. acetate, with the balance being butyralde- hyde acetal.
  • PVB resin is produced by known aqueous or solvent acetalization processes wherein PVOH is reacted with butyraldehyde in the presence of acid catalyst to produce PVB, followed by neutralization of the catalyst, separation, stabilization and drying of the PVB resin. It is commercially available from Monsanto Company as Butvar® resin.
  • Plasticized PVB as interlayer sheet at a thickness of about 0.13 to 1.3 mm is formed by mixing the PVB resin and plasticizer (and optional, additional, well-known property-enhancing additives) and then extruding the formulation through a sheeting die, i.e. forcing molten, plasticized PVB through a horizontally long vertically narrow die opening substantially conforming in length and width to that of the sheet being formed, or by casting molten polymer issuing from an extrusion die onto a specially prepared surface of a die roll in close proximity to the die exit to impart desired surface characteristics to one side of the molten polymer.
  • sheet formed of polymer cast thereon will have a rough surface on the side con ⁇ tacting the roll which generally conforms respectively to such valleys and peaks.
  • a rough surface on the other side can be provided by the design of the die opening through which the extrudate passes.
  • Such a die opening configuration is more particularly shown in Fig. 4 of U.S. No. 4,281,980.
  • Alternative known techniques of producing a rough surface on one or both sides of an extruding sheet involve the specification and control of one or more of the following: polymer molecular weight distribution, water content and temperature of the melt. Such techniques are dis ⁇ closed in U.S. Nos.
  • sheet of the invention may contain other additives such as dyes, pigments, ultraviolet light stabilizers, antioxidants, adhesion control salts and the like.
  • Pummel Adhesion measures inter ⁇ layer adhesion to glass.
  • Two ply glass laminates prepared as recited above for the MPV test were conditioned to -17°C and manually pummeled with a 1 pound (454g) hammer to break the glass. All broken glass unadhered to the PVB layer was then removed.
  • the amount of glass left adhered to the interlayer is visually compared with a set of standards of known pummel scale, the higher the number of the standard, the more glass remaining adhered to the interlayer - i.e. at a pummel of zero, no glass at all is left whereas at a pummel of 10, 100% of the interlayer surface is adhered to the glass.
  • Desirable impact dissipation occurs at a pummel adhesion value of 3 to 7, preferably 4 to 6. At less than 3 too much glass is lost whereas at more than 7 adhesion is generally too high and shock absorption is poor.
  • Yellowness Index Two ply glass lamin- ates with sample interlayer of 6.3 mm thickness were prepared as recited above. Yellowness Index (YI) was measured using a Hunter D54 Spectrophotometer.
  • PVB resin for admixture with the plasticizer blend had less than 3% residual acetate groups and a vinyl alcohol content of 18.2%. Exudation test results follow in Table 1.
  • the primary plasticizer was pure di(2-ethyl hexyl) adipate and, where used, the minor constituent, referred to as "coplasticizer” was the preferred monoester/castor oil mixture of 70% propylene glycol monoricinoleate, 30% castor oil.
  • PHR means parts total plasticizer per 100 parts PVB resin.
  • % reduc ⁇ tion refers to the decrease in exudation weight loss with coplasticizer over the control at equivalent loadings in the resin.
  • Control Example 12 contained 100% DHA.
  • Exs. 2, 4, 6, 8 and 9-11 illustrate signifi ⁇ cant reductions (in certain cases at least 15%, e.g. from 19 to 53%) in total plasticizer exudation weight loss when the preferred minor coplasticizer mixture constituent of the invention is present in a plasti ⁇ cizer blend with DOA.
  • the control Examples at 100% DOA confirm the unacceptable performance of DOA as a sole plasticizer in PVB resin. At 100%, sufficient DOA cannot be retained in the PVB resin to provide a glass transition temperature low enough for the plasticized mixture to be effectively used as an interlayer to absorb impact.
  • EXAMPLES 13-17 These illustrate alternative coplasticizer compositions in a blend with DOA. Coplasticizer content in the plasticizer blend in each case was 18% providing a 4.6:1 ratio of primary/coplasticizer.
  • the PVB resin was the same as in Examples 1-12. Results follow in Table 2. Castor oil is abbreviated "CO.”.
  • 'Flex 9 is propylene glycol lonoricinoleate 2
  • Flex 15 is ethylene glycol aonoricinoleate
  • control Example 20 was 100% DHA at 32 PHR.
  • CO in these Examples means coplasticizer.
  • This Example measures the edge stability after prolonged exposure to sunlight of interlayers containing the 75/25 DOA/CO plasticizer of Example 19 above in comparison with a DHA control.
  • ESN Edge Stability Number
  • ESN is a value obtained by an arbitrary method for calculating edge defects in a laminate which is proportional to the amount of total delamination attributable to the test interlayer for the nine laminate sample of that interlayer. More particularly, it is a mathematical summation of defect length times a weighting factor corresponding to the depth or distance of each defect from the edge of the laminate sample.
  • laminates containing the Ex. 19 inventive plasticizer formulation had no defects whatsoever and therefore an ESN of 0.
  • the ESN of laminates containing the DHA control had an ESN of 30.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Composition et feuille de ladite composition utilisée dans des vitrages stratifiés comprenant de la résine de polybutyral de vynil plastifié avec un mélange de a) adipate de dioctyle (ADO) et b) une quantité de réduction d'exudation de i) un ou plusieurs monoestères d'un glycol et un acide gras insaturé contenant 16 à 20 atomes de carbone comportant un groupe hydroxyle fixé à la molécule d'acide ou ii) de l'huile de ricin ou iii) un mélange de i) et ii), le rapport entre i) et ii) dans le mélange de iii) étant compris entre environ 1:1 et 5:1. Sur une base pondérale le mélange de plastifiant représente environ 65 à 95 %, de préférence 70 à 90 % de ADO et 35 à 5 %, de préférence 30 à 10 % de b).
PCT/US1991/004402 1990-07-02 1991-06-21 Polybutyral de vinyl plastifie et sa feuille formee WO1992000349A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US548,471 1983-11-03
US54847190A 1990-07-02 1990-07-02

Publications (1)

Publication Number Publication Date
WO1992000349A1 true WO1992000349A1 (fr) 1992-01-09

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MX (1) MX9100041A (fr)
WO (1) WO1992000349A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001014466A1 (fr) * 1999-08-19 2001-03-01 Danisco A/S Composition
US6949597B2 (en) 1999-08-19 2005-09-27 Danisco A/S Composition
EP2011771A4 (fr) * 2006-04-25 2012-03-07 Sekisui Chemical Co Ltd Film intermediaire pour verre stratifie et verre stratifie correspondant

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0054466A1 (fr) * 1980-12-02 1982-06-23 Saint Gobain Vitrage International Plastifiant pour polyvinylbutyral, application à la réalisation d'intercalaires pour vitrages feuilletés de sécurité et produits ainsi obtenus
US4563296A (en) * 1983-08-12 1986-01-07 Monsanto Company Plasticizer blend for polyvinyl butyral

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0054466A1 (fr) * 1980-12-02 1982-06-23 Saint Gobain Vitrage International Plastifiant pour polyvinylbutyral, application à la réalisation d'intercalaires pour vitrages feuilletés de sécurité et produits ainsi obtenus
US4563296A (en) * 1983-08-12 1986-01-07 Monsanto Company Plasticizer blend for polyvinyl butyral

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
WPI, FILE SUPPLIER, Derwent publications Ltd., London, GB, AN=79-05038b &JP-A-53140104 (BANDO CHEM IND) December 6, 1978 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001014466A1 (fr) * 1999-08-19 2001-03-01 Danisco A/S Composition
US6734241B1 (en) 1999-08-19 2004-05-11 Danisco A/S. Composition
US6949597B2 (en) 1999-08-19 2005-09-27 Danisco A/S Composition
EP2011771A4 (fr) * 2006-04-25 2012-03-07 Sekisui Chemical Co Ltd Film intermediaire pour verre stratifie et verre stratifie correspondant
EP2937215A1 (fr) * 2006-04-25 2015-10-28 Sekisui Chemical Co., Ltd. Film intercalaire pour verre feuilleté et verre feuilleté

Also Published As

Publication number Publication date
AU8239191A (en) 1992-01-23
MX9100041A (es) 1992-02-28

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