CA1101743A - Organo silane coupling agents - Google Patents

Organo silane coupling agents

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Publication number
CA1101743A
CA1101743A CA224,840A CA224840A CA1101743A CA 1101743 A CA1101743 A CA 1101743A CA 224840 A CA224840 A CA 224840A CA 1101743 A CA1101743 A CA 1101743A
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CA
Canada
Prior art keywords
glass fibers
organo
cementitious
silane
composition according
Prior art date
Legal status (The legal status 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 status listed.)
Expired
Application number
CA224,840A
Other languages
French (fr)
Inventor
Kevin M. Foley
Homer G. Hill
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Owens Corning
Original Assignee
Owens Corning Fiberglas Corp
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 Owens Corning Fiberglas Corp filed Critical Owens Corning Fiberglas Corp
Application granted granted Critical
Publication of CA1101743A publication Critical patent/CA1101743A/en
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/1025—Coating to obtain fibres used for reinforcing cement-based products
    • C03C25/103—Organic coatings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/04—Esters of silicic acids
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/24—Coatings containing organic materials
    • C03C25/26—Macromolecular compounds or prepolymers
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/24—Coatings containing organic materials
    • C03C25/40—Organo-silicon compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Surface Treatment Of Glass Fibres Or Filaments (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

ABSTRACT OF THE DISCLOSURE

Organo silane coupling agents having at least two hydro-lyzable silane groups are disclosed. Glass fibers coated with these organo silanes are suitable for reinforcing cementitious materials.

Description

-This inven~ion relates to silane coupling agents. lt also relates to glass fibers coated with the coupling agents.
The coated fibers are suitable for reinforcing cementitious materials.
In the past, the use of glass fibers for long term ~5 or more years) reinforcement of cementitious materials having a high alkali content has had limited success. The harsh alkali envlronment degrades the types of glass fibers commonly used to reinforce plastics. This alkali attack and subsequent ~iber strength loss generally so weakens the fibers that long term reinforcement of a cementitious matrix by such fibers is neither predictable nor dependable.
To remedy this situation the prior art has tried a number of potential solutions. One is to coat the fibers with some material that is alkali resistant. Epoxy resin coated fibers, for example, generally will withstand alkali attack.
Another potential solution is to use a high alumina cement which has less alkali content. Still another solution is to formulate a glass composition which in fiber form will be resistant to ~20 alkali a~tack.
We now have discovered organo silanes having at least two hydrolyzable silane groups. We believe that the distance between any two hydrolysis sites on a glass fiber is greater than the distance between any two hydrolyzable silane groups in the organo silanes of this invention. Hence, the organo sil- -ane only sees one hydrolysis site on the glass fiber. This neces-sarily frees up at least one hydrolyzable silane group to bond to a hydroly~is site in a cementitious matrix.
Accordingly, the present invention in one aspect pro-vides a composition consisting of glass fibers having on their surfaces a coating of organo silanes containing at least two F
. .

7~3 hydrolyzable silane groups wherein the distance between any two of said hydrolyzable silane groups is less than the distance between any two hydrolysis sites on said glass fibers.
Another feature of the invention is the provision of glass fibers coated with these organo silanes.
A further aspect is the provision of cementitious mate-rials reinforced with such coated glass fibers.
The organo silanes of this invention contain at least two hydrolyzable silane groups. Specific examples of these sil-anes are: ~
Cl Cl CH3 Cl Cl ~ ~.
(1) (CH3 CH CH20)3 SiOCH2CH CH20 ~ C ~ OCH2CH CH20 SilOCH2CH CH3)3 Cl Cl Cl Cl
(2) (CH3CH CH20)3 SiO CH2CH CH20 ~ OCH2 CH CH20 Si(OCH2 CH CH~)3 .
(3) (C~30)3 Si CH2 CH2 Si(OCH3)3
4) (CH30)3 Si ~
~20 ~ ~ CH2 CH2 Si(OCH3)3 ;
(5) (CH3CH20j3 Si CH2 CH2 SCH2 CH2CH2Si(OCH3)3 ~ , ` .
(6) (CH30)3 Si CH2 ~ ~ CH CH2 SilOCH3)3 C~3 '
(7) (CH30~3Si~ CH2CH2 ~ ~.
~ CH2CH2Si(OCH3)3 F
, , . .. . -\
79~3 We employ various methods to produce these organo silanes.
For example, heating a mixture of vinyltriethoxysilane and gamma-mercaptopropyltrimethoxysilane produces silane no. (5). We pre-pare silane no. (3) by first reacting vinyltrichlorosilane with trichlorosilane in the presence of a platinum catalyst and then reacting the reaction product with a mixture of methanol in pen-tane. The latter reaction is exothermic.
Any commercially available glass fibers, such as those produced from E glass, can be used in the practice of this inven-tion. However, we prefer to use al~ali resistant glass fibers,especially calcium hydroxide resistant glass fibers. Alkali-resistant glass fibers that can be employed include those dis-closed in British Patent Specification Nos. 1,243,972 (issued to National Research and Development Corp. and published August 25, 1971) and 1,290,528 (issued to Pilkington Bros. Ltd. and pub-lished September 27, 1972), and in United States Patent 3,840,379 issued October 8, 1974. The ZrO2 and TiO2 containing composi-tions described in U.S. patent 3,840,379 provide a unique combi-nation of alkali-resistance, low liquidus temperature and desi-rable viscosity for the fiberization of glass compositions andfor the reinforcement of cementitious materials. The glass com-positions of U.S. patent 3,840,379 have the following range of proportions by weight: sio2 1 60 to 62~; CaO, 4 to 6%; Na2O, 14 to 15%; K2O, 2 to 3%; ZrO2, 10 to 11% and TiO2, 5.5 to 8%.
E glass is a textile glass composition used for many years for the reinforcement of non-alkali matrices such as plas-tics. It is well known for its properties which allow it to be easily and economically fiberized in commercial quantities and at commercial rates using direct melt furnaces and fiberizing tech-3~ niques. Typically, E glass has the following composition in per-cent by weight:
3 ~

.
" . , , :
- . . .. . .: . - .

~1~179~3 Ingredi,entE g~ass SiO2 54 . 6 Al203 14.5 CaO 18.0 MgO 4.0 B203 6.9 Na20 0 4 TiO2 0.6 F2 0.6 Fe203 0-4 The coated glass fibers of this invention can be success-fully used as a reinforcing material in various cementitious pro-ducts or matrices including cement, Portland cement, concrete, mortar, gypsum, and hydrous calcium silicate.
The term hydrous calcium silicate denotes crystalline compounds formed by the reaction of lime (CaO), silica (SiO2) and water. Two hydrous calcium silicates generally of interest are:
tobermorite, having the formula 4 CaO 5 SiOz 5 H20; and zonot-lite, having the formula 5 CaO 5 SiO2 H20. Hydrous calcium ' ~ 20 silicate products often are used as heat insulation materials.
The coated glass fibers of this invention can be used alone or in combination with asbestos fibers, mineral wool or organic fibers such as wood fibers in the production of cementi-tious products, especially calcium silicate products.
The organic materials are cellulosic type materials such as pulp fiber, cotton, straw, bagasse, wood flour, hemp, rayon, j .
coir fiber and the like.

We apply a uniform coating or layer of the organo silane to the surface of the glass fibers. By the expression "uniform coatinq or layer" we mean that all points on the surface of the .

, , .

glass fibers are covered with a coating at least monomolecular in thickness. The uniform coating can be applied by spraying, dip-ping, brushing or the like. A uniform coating is essential when the glass fiber is to be used in a hostile environment. An un-coated area on the glass fiber surface would be subject to alkali attack at the unprotected spot. This would result in destruction of the fiber and the end of the fiber's utility as a reinforcing agent in a cementitious medium. The amount of organo silane on the surface of the glass ranges from 0.001 to 10.0% by weight of glass and silane. Preferably, the amount of organo silane ranges from 0.003 to 5.0~. In actual practice the only limit to the upper concentration is economics. A monomolecular layer is suff-icient to provide the protection required. Multiple layers are unnecessary and wasteful.
Present technology allows for the production of glass fibers having a diameter ranging from 0.0001 inch to 0.~004 inch at a rate of 10,000 feet to 15,000 feet per minute. Glass fibers are produced from small streams of molten glass which exude through tiny orifices located in what is called a bushing. Typi-cally, bushings have 204 such orifices. The tiny streams of mol-ten glass which issue from the bushing are attenuated by pulling the fibers until the diameters given above result, and during which time the streams cool and solidify into what are called filaments.
A further advantage of using the organo silanes of this invention is the variety of means of application which can be em-ployed. The solution may be applied at the bushing to the bare glass fibers before they are gathered into a strand. The applic-ation may be deferred until the gLass fibers are gathered into a strand thereby applying the solution to the bare strand.

:

, , , , ,, , . , , , . ~ .
:
. .

Alternatively the solution may be applied to a strand which has been treated previously with a coating composition. Another option is to use the aqueous ammonium zirconyl carbonate as a component with other coating compositions. This mixture of coating compositions may be applied using any of the above des-cribed means. The coated strand may be dried before collection as a package by passing it through a tube furnace. Alternatively, the coated strand may be wound and collected as a package and then placed in an oven for drying.
In the past, asbestos fibers have been very successful as a reinforcement for many types of inorganic matrices because of their characteristics and ability of the asbestos fibers to dis-perse and to provide some entangled network. The entangled net-work is generally thought to be due to the non-uniformity of the length of the asbestos fibers, ranging anywhere from 1/16 inch to 4 inches in length. In order to employ glass fibers as a suit-able replacement for asbestos fibers, it is generally thought that some of the characteristics possessed by the asbestos fibers should be obtained with glass fibers. For this reason the length of the glass fibers may range from 1/8 inch to about 2 inches in length and preferably from 1/2 inch to 1 inch in length in order to obtain some entanglement of the glass fibers upon dispersion of the glass fibers in the inorganic matrix. Furthermore, many inorganic matrices are susceptible to crack propagation. sy the use of these longer fibers the fibers traverse the cracks thereby adding strength to the matrix. Blends of various lengths of glass fibers also can be employed.
If desired, other sizings, silanes, lubricants and the like also can be applied to the glass fibers.
The advantages of this invention are illustrated by the following examples. The reactants, proportions and other speci-fic conditions are presented as being typical and should not be fB

.

construed tv limit the invention unduly.

EXAMPLE I
Cl Cl CH3 Cl Cl (CH3CH CH20)3 SiO CH2 CH CH20 ~ C ~ OCH2 CH CH2Q SilOCH2 CH CH3)3 was prepared by reacting 3 moles of propylene oxide, 1 mole of silicon tetrachloride and 0.5 mole of 10CH2 - CH CH20 ~ CH~ O CH2 CH - CH2 at a temperature of 175F for a time of 16 hours.

E ~ MPLE II
Cl Cl Cl Cl :
/ \ I I
~ CH3 CH CH20)3 SiO CH2 CH CH20 ~ OCH2 CH CH20Si (OCH2 CH CH3)3 was prepared according to the procedure of Example I except that the propylene oxide and silicon tetrachloride were reacted with -0.5 mole of /\ /
~` CH2-CH CH20 ~ OCH2 CH-CH2 ,~ ' ' ' ' ~
EXAMPLE III

(CH30)3 Si CH2 ~ CH CH2 Si(OCH3)3 ` CH3 :.
;~ was prepared by reacting 0.75 mole of d-limonene, 1.6 moles of trichlorosilane and 1 ml of a solution containing 10 grams of chloroplatinic acid in 150 ml of isopropanol. This was heated to reflux for 3 days. The reflux temperature rose to 179C.
' ~ .

Five hundred ml of pentane then were added to the reaction, fol-lowed by a solution of 5.82 moles of methanol in 100 ml of pen-tane. This was distilled giving 145 grams of material koiling from 100 to 200C at 2 mm of mercury.

EXAMPLE IV
(CH3~)3 si CH~ CH2 Si (OCH3)3 was prepared according to the procedure of Example III except that 1.5 mole of vinyltrichlorosilane was employed in place of d-limonene.

EXAMPLE V
(CH30)3 Si ~
~ CH2 CH2 Si (OCH3)3 was prepared according to the procedure of Example III except that 4-vinylcyclohexene was employed in place of d-limonene.

EXAMPLE VI
(CH3 CH2 0)3 Si CH2 CH2 SCH2 CH2 CH2 Si (OCH3)3 :; .
was prepared by reacting 2.28 moles of vinyltriethoxysilane and 2.28 moles of gammamercaptopropyltrimethoxysilane. The reaction was heated to 150C and maintained at that temperature. After 48 hours the reaction was stopped.

~: ~
EXAMPLE VII
(CH30)3 Si CH2 CH2 ~
CH2 CH2 Si (OCH3)3 .~ ~
was prepared by reacting 2 moles of vinyltrichlorosilane, 1 mole of benzene and a small amount of aluminum chloride. This was `: :
~` 30 ~ heated to reflux for 1 day. One thousand ml of pentane then were : ` :

~ 8 .

: - :

added to the reaction. This was followed by a solution of about 6 moles of methanol in 100 ml of pentane. The product can be used as is or distilled.

EXAMPLE VIII
Glass fibers were formed from the following glass compos-ition:
Ingred1,entsWe~ght Per~cent sio2 61.1%
CaO 5.1%
Na2O 14.4%
K2O 2.6~
ZrO2 10.4%
TiO2 6.0%
The fibers were gathered together as strands and passed through a bath of the silane of Example VII. While still wet, the coated strands were passed through an aqueous bath of 10%
;~ solids of aluminum silicate. The strands then were passed through a tube furnace heated to 500F~ The furnace was 4 feet in length and a strand requires 10 to 30 seconds to pass through it. The strands were dry upon exit and the resulting coatings were at least monomolecular in thickness. Upon exit from the furnace the strands were collected and wound to form a package.

~:
EXAMPLE IX
The process of Example VIII was repeated except that the silane of Example III was employed instead of the silane of Example VII and that the aluminum silicate bath was not employed.

: :

.

` ~:
- , . . .

EXAMPLE X
Various samples of the coated glasses of Examples VIII
and IX and bare glass strands (control) were tested as follows.
A layer of cement about 3/8" thick was applied to a tongue de-pressor. The cement has a water/cement ratio of 0.33. One-half inch of a length of glass strand is immersed about halfway into the wet cement. A tail is left protruding. The cement then was cured at 100% relative humidity for the time indicated in the following table. The samples were mounted in an Instron and the glass strand was broken or pulled out of the cement. The break or pullout loads ranged from about 5 to 16 pounds. A high per-centage of breaks indicates good coupling between the glass and cement. A low percentage of breaks indicates pullout and poor coupling between the glass fiber and cement. The results were as follows:
P7~RC~NTA GE OF BREAKS

Time Bare G~ass SiZane Si~ane (~ee~s) (controZ) (E~. VII) (Ex. III) 1 30 100 --*

2 ~5 100 B3 - 4 4~ 100 --*
16 61 100 --*
*not carried out ~; ~his data reveals the marked advantage of the silane coupling agents of this invention. Glass fibers coated with these coup-ling agents are very suitable for reinforcing cementitious mat-erials.
While the invention has been described in considerable detail, we do not wish to be limited to the particular embodi-ments shown and described, and it is our intention to cover , ~ ' .

~1743 hereby all novel adaptations, modifications and arrangementsthereof which come within the practice of those skilled in the art to which the invention relates.

~: 20 .

:;~ ' ;-, ' , :

:

,....

, ,

Claims (20)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
1. A composition consisting of glass fibers having on their surfaces a coating of organo silanes containing at least two hydrolyzable silane groups wherein the distance between any two of said hydrolyzable silane groups is less than the dis-tance between any two hydrolysis sites on said glass fibers.
2. A composition according to claim 1 wherein said organo silane has the formula .
3. A composition according to claim 1 wherein said organo silane has the formula
4. A composition according to claim 1 wherein said organo silane has the formula (CH30)3 Si CH2 CH2 Si (OCH3)3.
5. A composition according to claim 1 wherein said organo silane has the general formula .
6. A composition according to claim 1 wherein said or-gano silane has the formula (CH3 CH2 0)3 Si CH2 CH2 SCH2 CH2 CH2 Si (OCH3)3.
7. A composition according to claim 1 wherein said organo silane has the general formula .
8. A composition according to claim 1 wherein said organo silane has the general formula .
9. Glass fibers having on their surfaces a uniform coating at least monomolecular in thickness of organo silanes as defined in claim 1.
10. Glass fibers as defined in claim 9, wherein the amount of organo silanes ranges from 0.0001 to 10.0% by weight of glass fibers and organo silanes.
11. Glass fibers as defined in claim 9, wherein the amount of organo silanes ranges from 0.003 to 5.05 by weight of glass fibers and organo silanes.
12. Coated glass fibers as defined in claim 9, in which the fibers are alkali-resistant glass.
13. Coated glass fibers as defined in claim 9, in which the coating includes aluminum silicate.
14. A cementitious product comprising a composite of reinforcing materials on a cementitious matrix wherein one of the reinforcement materials comprises coated glass fibers having on their surfaces a coating of organo silanes containing at least two hydrolyzable silane groups wherein the distance between any two hydrolysis sites on a glass fiber is greater than the distance between any two hydrolyzable silane groups in the organo silanes.
15. A cementitious product as defined in claim 14, wherein the surface coating includes aluminum silicate.
16. The cementitious product of claim 14, or 15, where-in said cementitious matrix is Portland cement.
17. The cementitious product of claim 14, or 15, where-in said cementitious matrix is hydrous calcium silicate.
18. The cementitious product of claim 14, or 15, where-in said cementitious matrix is concrete.
19. The cementitious product of claim 14, or 15, where-in said cementitious matrix is cement.
20. The cementitious product of claim 14, or 15, where-in said cementitious matrix is mortar.
CA224,840A 1974-05-24 1975-04-17 Organo silane coupling agents Expired CA1101743A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US47310274A 1974-05-24 1974-05-24
US473,102 1974-05-24

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CA1101743A true CA1101743A (en) 1981-05-26

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JP (1) JPS5113724A (en)
BE (1) BE829103A (en)
CA (1) CA1101743A (en)
DE (1) DE2517601A1 (en)
FR (1) FR2272100B3 (en)
GB (1) GB1510801A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022059961A1 (en) * 2020-09-21 2022-03-24 주식회사 쎄코 Compound for ultra-thin strength-reinforcing coating agent, and strength-reinforcing coating agent comprising same

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Publication number Priority date Publication date Assignee Title
JPS54114281U (en) * 1978-01-31 1979-08-10
US4207071A (en) * 1979-02-01 1980-06-10 Dow Corning Corporation Durable modification of fibrous substrates using a polyoxyethylene-containing silane and articles therefrom
NZ303624A (en) * 1995-03-08 1999-01-28 Du Pont Reactive organosilicons as coatings, adhesives, and sealants
FR2738241B1 (en) * 1995-09-01 1998-03-20 Vetrotex France Sa REINFORCING GLASS WIRES AND CORROSIVE RESISTANT COMPOSITES
US6080816A (en) * 1997-11-10 2000-06-27 E. I. Du Pont De Nemours And Company Coatings that contain reactive silicon oligomers
US6329489B1 (en) 1999-12-20 2001-12-11 E. I. Du Pont De Nemours And Company Process for producing reactive silane oligomers
BRPI0802008A8 (en) * 2008-05-09 2017-12-26 O Nascimento Engenharia E Consultoria Ltda MANUFACTURING PROCESS OF FIBERCEMENT COMPOSITES USING CEMENTIUM MATERIALS REINFORCED WITH INORGANIC FIBERS CHEMICALLY MODIFIED BY ORGANOSILANES
CN103204871B (en) * 2012-01-13 2015-11-18 中国科学院化学研究所 A kind of sulfur-bearing bridging silesquioxane monomer and preparation method thereof and application
JP6067435B2 (en) * 2013-03-15 2017-01-25 東洋ゴム工業株式会社 Rubber composition and pneumatic tire
JP2017149824A (en) * 2016-02-23 2017-08-31 Ｊｘｔｇエネルギー株式会社 Silane compound, and rubber composition, sealing agent composition, adhesive composition and tire containing the same

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3759968A (en) * 1971-05-17 1973-09-18 Gen Electric Silyl maleates and polysiloxane maleates
US3816235A (en) * 1972-08-18 1974-06-11 Owens Corning Fiberglass Corp Glass fiber size composition

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022059961A1 (en) * 2020-09-21 2022-03-24 주식회사 쎄코 Compound for ultra-thin strength-reinforcing coating agent, and strength-reinforcing coating agent comprising same

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GB1510801A (en) 1978-05-17
FR2272100B3 (en) 1979-07-06
FR2272100A1 (en) 1975-12-19
DE2517601A1 (en) 1975-12-04
BE829103A (en) 1975-09-01
JPS5113724A (en) 1976-02-03

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