JPH08113644A - Silylated polyamine polymer and chemically processed composition using same - Google Patents

Abstract

PURPOSE: To provide a chemical treating compsn. which can improve the lubricity and tensile strength of a substrate by reacting a specific polyamine-contg. polymer with an amine-reactive organoalkoxysilane (hydrolyzate).

CONSTITUTION: A water-dispersible polyamine-contg. polymer having at least one kind of free amino group and selected from among polyamines having free amine parts and acid parts of a polyfunctional fatty acid material, condensates of polyfunctional acids and polyamines, polyamines having chain- extended fatty acid parts, acylated polyalkyleneamines, condensates of a polyamine, a fatty acid, and a dimer acid, and polyamine polyamides obtd. by condensing a polyamine of the formula: H₂N(C_nH_2nNH)_xH (wherein n is 2-6; and x is 2-6) having at least three amino groups with a monofunctional acid, is reacted with an amine-reactive organoalkoxysilane (hydrolyzate) at a temp. of room temp. to 70°C for 15 min to 8 hr.

COPYRIGHT: (C)1996,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a treatment composition which may be present on a substrate such as a fiber, a material in which a cationic lubricant and a silane material alone and in combination with other components are present, as well as the preparation of said composition. Methods and treated substrates.

[0002]

BACKGROUND OF THE INVENTION A variety of nonionic lubricants are available for a wide range of applications, most of them containing a lubricant that eventually contacts one or more substrates. For example, nonionic lubricants such as hydrogenated vegetable oils and cationic lubricants such as partially amidated polyamines and acrylated alkyl imidazolines are good fiber lubricants. Fiber lubricants are formulated with other components into treatment compositions for application to the fibers. The composition may be sized to process glass fibers during the formation of bundles or strands to form bundles or strands of fibers. In the manufacture of glass fiber strands that are twisted to form yarns, the preferred size is starch oil size. This size provides protection throughout the precise formation of fiber bundles or strands and the twisting of one or more bundles to form yarns and is removed from the finishing fabric during the heat treatment step. It is a thing.
In addition, fiber lubricants are useful in sizing over fibers that reinforce the polymer matrix in the manufacture of fiber reinforced plastics. In this application, the size can once again provide protection and also an affinity between the fiber and the matrix polymer or resin. Lubricants and sizing components are generally attached to the fibers during their formation and protect the fibers through successive processing steps. These processes include winding fibers and strands into homing packages, drying water-soluble or solvent-based sizes to remove water or solvents, twisting from one package and transferring to bobbins, usually warp in fabrics. Beaming to transfer the twisted yarns into a very large package used as and chopping in wet or dry state
Or roving into larger bundles or groups of strands.

[0003]

The formulation of sizing in such applications must be flexible to adequately supply the required properties, and consistent with each other to achieve the desired properties. Must have ingredients that do. For example, as size, it is known that the use of organosilane ester coupling agents and their hydrolyzed derivatives can improve the tensile strength of sized glass fiber strands. Unfortunately, while providing such improvements, organosilane materials can result in imperfections in woven or fabrics made from strands. When the strand woven fabric or fabric with the organosilane coupling agent is heat cleaned to remove certain or all chemical treatments, deposits or residues may remain on the fabric or fabric. This imperfect nature can cause losses in the use of woven fabrics and fabrics.

It is an object of the present invention to provide lubricious properties and also to have low, if any, harmful deposits or residues on the fibers or strands of the formulation which have been heat-cleaned to remove the tensile strength. To provide a chemical composition capable of providing a formulation for application to substrates such as improved fibers.

[0005]

SUMMARY OF THE INVENTION From the following disclosure, the above-mentioned object and another object are to obtain a fatty acid moiety.
and one or more polyamines having free tertiary and / or secondary amines (hereinafter "polyamine I") and one or more amine-reactive organofunctional silane esters and / or It is accomplished by a chemical reaction product with the hydrolysis product.

The reaction product can be formed by adding the reaction components in any order in a suitable molar ratio to produce a silylated reaction product polymer (hereinafter "silylated RP polymer"). To be done. Silylated R
The P-polymer can have a cationic amine lubricity with a residual amine number in the range of about 200 to 800 and a residual acid number in the range of up to about 20 and is hydrolyzable or It has an organosilane moiety with partially or fully hydrolyzed groups.

The polyamine I reaction components include polyalkylamine condensation products having polyfunctional acids, some of which include fatty acids, and / or polyamine condensation products, and / or amidoamine polymers such as acylated polyamines. And / or polyamines with polyamine-polyamides having acid moieties and free amines as well as polyalkyleneimines. The amine-reactive organofunctional silane ester or its hydrolysis product (hereinafter "amine-reactive silane") generally has the formula: Xa-Si (OR) _b .

X is an organic residue having an amine-reactive moiety.

By using the term "amine-reactive" for said moiety, to the organofunctional moiety of the compound whose organofunctional-alkoxysilane or its hydrolysis product is capable of reacting with the amine moiety of Polyamine I, By polyamine I is meant having or capable of having one or more reactive moieties capable of reacting with the active hydrogens present on residual amines, which are epoxy or glycidyl groups, isocyanate groups, Ester group,
It may be selected from moieties such as haloalkyl groups and acryloxy groups. The term is also meant to include organofunctional alkoxysilanes that can be made reactive to Polyamine I by using a reaction aid that is not amine reactive in nature. In addition to amine-reactive moieties, said organic residue is an alkyl residue such as a saturated alkyl residue having 1 to 6 carbon atoms, an alkylaryl residue containing 6 to 10 carbon atoms, a cycloalkyl It may have a residue or an aryl residue. a is an integer of 1-2, and b is 4-
It is an integer equal to a. R ₁ is an alkyl residue having 1 to 6 hydrogen atoms, an alkylaryl residue having 6 to 10 carbon atoms, a cycloalkyl residue, or an aryl residue, and b is greater than 1. Sometimes it is a mixture of hydrogen atoms and one of these organic residues.

Another aspect of the present invention is that the silylated RP polymer is present by itself or at least with water in a major amount for use as a water-soluble based chemical treatment composition for the substrate. is there. The type of substrate can range from any form of glass substrate, including glass plates, fibers, etc., to organic substrates, such as fibers. Another aspect of the invention is to prereact one or more polyamine I with one or more amine-reactive silane to produce a silylated RP polymer,
Using a fiber lubricant comprising formulating the pre-reactant into a chemically treated composition using at least a predominant amount of water, applying the formulated composition to fibers, and focusing the fibers into a bundle of fibers. It is the method of treating the old fiber.

[0011]

EXAMPLES Polyamine I, which is suitable for the preparation of silylated RP polymers, can be obtained from several different reaction components. For example, a fatty acid material in the presence or absence of dimer acid, which comprises polymerized fat acid because the polyamine and / or polyalkylene polyamine and / or polyalkylene imine has at least one fatty acid moiety and at least one fatty acid moiety. (Fatty acid material). In one aspect of the invention, the dimer acid is used in a sufficient amount and has polyamine I having lubricant properties and at least sufficient free amine and / or acid to be dispersible in water. It is of the type that occurs. The polyamine I lubricant may be one that forms a fluid film type lubrication at the interface of the two substrates. The substrate can be a bundle of fibers of glass fibers having a diameter in the range of 4-30 microns or more. Lubricants are required because such bundles or strands are subject to loads and forces during processing and handling.

An example of a non-exclusive state was to wind a strand of fiber into a tubular annular package of fiber bundles without fiber breakage or powder generation. The lubricant is formulated with Polyamine I itself or other ingredients and provided through its use.

A preferred example of polyamine I is one or more polyalkyl polyamines reacted with fatty acids containing partially amidated polyamines, wherein the polyamine prior to amidation is US Pat. No. 3,597, Two
It can have a molecular weight of about 50,000 or higher as described in US Pat. A preferred commercially available partially amidated polyalkylene polyamine is Emery-6717, wherein the polyamine is
It is a polyethyleneimine having a molecular weight of about 1200 and a residual amine value in the range of up to about 400, and is available from Henkel (Emery Group, North Lake Drive 11501, Cincinnati, Ohio). Another preferred example is the condensation product of one or more polyamines with other fatty acids with or without dimer acids, such as Versamide and Genamide resins. And these are Henkel Corp. (Polymer Division, 60525 South 9th Avenue 53, Lagrangian, Illinois).
25). In particular one of these Versamides 140 has a viscosity at 25 ° C. of 116 poise, weighs 8.1 lbs / gallon, and 10
It has a solid content concentration of 0%, a specific gravity of 0.970, and 7
It has no volatility at 0 ° F (21 ° C) and a flash point of 3
Greater than 65 ° F (185 ° C). Processes for the preparation of such polyamides are described, for example, in Peermann.
Man, et al., U.S. Pat. No. 2,881,194.

In addition, polyethyleneamines such as acrylated polyethylamine can also be used. It is prepared, for example, from linear poly-2-oxazoline with an alkyl substituent in the 2-position. The alkyl substituent is 1 to 1
It can be of 7 carbon atoms and the degree of polymerization is about 8 to
It can be 22.

Condensation products of polyamines with fatty acids with or without other dimer acids have many isomers,
One of them can have the following structure;

[0016]

Embedded image

Wherein R is an aliphatic residue having about 14 to about 34 carbon atoms, preferably about 26 to about 34.
An unsaturated alicyclic bifunctional residue having carbon atoms, n is an integer in the range 0 to about 3, preferably 2, and m is about 1 to 15, preferably about 1 to 1. Within the range of 2.

As stated above, the polyamine I of the above structural formula
Can be obtained, for example, by condensation of polyamines with dimerized fatty acids. Polyamines include, for example, 2
Those which may consist of alkylamines having from about 8 carbon atoms can be used, such as ethylenediamine, diethylenetriamine, tetraethylenepentamine or triethylenetetraamine. Another type of useful polyamine is available as polyalkylene polyamines, which are commercially available mixtures of polyalkylene polyamine congeners. For example, polyethylene polyamines can be used, and polyalkylene polyamines using ethylene and propylene groups can also be used. Such mixed polyalkylene polyamines can be readily condensed with ethylene diamine with one or more proportions of acrylonitrile and reduced to form mixed alkylene polyamines, for example, by catalytic hydrogenation to form N-cyanoethyl ethylene diamine. Preferred dimerized fatty acids for preparing such condensation products may be prepared from unsaturated fatty acids having 8 to 18 carbon atoms, such as myristoleic acid, palmitoleic acid, oleic acid. , Linoleic Acid and Encyclopedia of Chemical Technology (Encyc
lopedia of Chemical Techn
second edition, Kielkor Osmer (Ki)
rkaol Othmer), Volume 8, 811-856.
Page, Interscience Publishers (Inte
rScience Publishers), New York (1965), fatty acids containing monoethenoid and polyethenoid compounds, and a method for producing the same.

Another preferred polyamine I is a chain-extended polyamine which may or may have the reaction product of a fatty acid or dimer acid. Such materials may generally be prepared from the following reaction components in the reactions described below.

(I) NH ₂ = (R-NH) _x -R-NH ₂ (II) (Q) _p R'-R ¹ -R '(Q) _p (III) CH _3- (CH ₂ ) _y -COOH (I), (II), (III) is reacted as a reaction component,

[0021]

[Chemical 4]

A mixture of and (VI). (VI)
Is one of (VII), (VIII), and (IX) shown below.
Or (IV) and / or (V) having a moiety of a repeating unit containing a branched chain as described above.

[0023]

Embedded image

[Wherein (1) p, w, x, y and z are integers, p is 1 or 0, x and y are values that can be placed in the reactant, and w and z are up to about 50,000. A value for giving a molecular weight (Mw), preferably for giving a molecular weight (Mw) up to about 10,000 in order to maintain an appropriate viscosity, R is a lower alkyl group, R'is a carbonyl group,
Selected from alkyloxirane groups and diisocyanate groups, R ¹ is alkylene, a bifunctional alkyl and / or bifunctional aryl residue having 2 to 15 carbon atoms and Q is OR or a halide, R ′ ^* Is a cleaved oxirane group or a urea functional group obtained by reacting an isocyanate with an amine, wherein when R ¹ is a carbonyl group, Q is OR or a halide, and R ′ is a lower alkyl group. At this time, Q is a halide, and when R'is an oxirane group, P = O. (2) Preferably (I) is present in a slight excess to control the molecular weight. This reaction has structure (V)
Is a preferred lubricating material and therefore leads to its yield and manufacturing advantages. Preferably, structure (IV) is a non-lubricated structure and is a reaction product having an unreacted amine value, so that its formation is kept to a minimum. This gives the effect that unreacted secondary nitrogen groups in the reaction product improve the dispersibility in water.

(3) Since all the reaction components can be liquid, the reaction can be carried out as it is. However, if the viscosity of a certain reaction component or reaction product is too high, heat or use an organic solvent such as alcohol. Can be used for dilution. Depending on the particular type of chain extender, it can be other than alcohol when the solvent is an organic solvent.

For example, in (I), NH ₂ — (CH ₂ —
_{CH 2 -NH) 3 -CH 2 -CH} 2 -NH 2; (II)
In _{C 2 H 5 O (O)} C-CH 2 -CH 2 -C (O) O
C ₂ H ₅ and (III) CH ₃ (CH ₂ ) ₆ CO
It is OH.

Preferably, the reaction is carried out with the addition of (I) and (II) followed by the addition of (III) in order to give mostly structure (V) than the mixture of other structures.

The reaction involving the removal of by-products gives a mixture of structure (V) shown below with some cyclized and / or branched derivatives.

[0029]

[Chemical 6]

And here, the structure in which z is 0 is

[0031]

[Chemical 7]

It is

In addition to the linear structure described above, some of the moieties in the reaction product may be cyclized and / or branched. Cyclization can occur because two adjacent amines can react with fatty acids. The reaction product can be a mixture of all these structures.

As a non-exclusive example for the structures described above, and generally for the polyamines used in Polyamine I, the polyamines generally have 3 or more amine groups and have the general structural formula H _{2 N- (C n H 2n NH} ) x is -H example, wherein n is from about about 2 to 6, preferably in the range 2
And / or 3 and X can be any substance in the range 2-28 or higher, and preferably about 6 or higher. The polyamine may also contain minor amounts of dimers such as ethylenediamine and the like. The preparation of these materials is well known in the art. For example, the desired alkylene polyamine results from the reaction of a suitable alkylene dihalide with ammonia. Suitable examples of polyalkylene amines include diethylene triamine (DETA), triethylene tetramine (TETA),
Tetraethylene pentamine (TEPA), pentaethylene hexamine (PEHA), dipropylene triamine (DPTA), tripropylene tetramine (TPT)
A), tetrapropylenepentamine (TPPA), pentapropylenehexamine (PPHA), and dihexamethylenetriamine (DHMTA). Since these materials are commercially available and most are available as a mixture of isomers, this mixture of alkylene polyamines, as well as a single polyamine, is suitable for the preparation of the silylated RP polymers of this invention. Can be used for

Polyfunctional but predominantly difunctional organic compounds useful as chain extenders are polyfunctional compounds whose predominantly difunctional moieties are nitrogen via the active hydrogen of the residual amine of the polyamine. It is a compound capable of reacting with and forming a covalent bond. The term chain extender, in addition to the above properties, means that the reaction of the polyfunctional organic compound increases the molecular weight of the polymerization reactant primarily through its two functional groups due to molecular crosslinking. The reaction between the chain extender and the polyamine can be any primary and / or primary amine group at or at the end of the polyamine backbone.
Or it can occur with secondary amines. The reaction conditions and reaction components are preferably chosen such that the reaction yields highly branched, small amounts, no more than about 50% of the reaction product. These predominantly difunctional organic compounds are generally liquids or solids that melt at temperatures below about 200 ° C. and can generally be saturated materials. Some of these compounds also have an imidazoline group structure within the RP polymer. Chain extenders are predominantly difunctional in their reaction with polyamines, but there may be small amounts of polyfunctional organic or organic compounds that can react bifunctionally with polyamines. Particularly suitable chain-extending organic compounds are:
In the structure (X-R ₁ -Y), R ₁ is alkylene, preferably a bifunctional alkyl and / or aryl group having from about 2 to about 15 carbon atoms, and X and Y are each the same or Carboxylic acids and / or esters and / or anhydrides, epoxides, also known as glycidyl or oxirane, such as halides, alkyl halides and acid chlorides, diepoxysides, dihalides, dichloric acids and / or
Or those that are functional moieties that are isocyanates that can be diisocyanates. More specific examples are glycidyl ethers such as bisphenol A diglycidyl ether and butanediol diglycidyl ether,
Includes novolac epoxy, dichloroethane, dichloropropane, etc. Also, the length of the carbon chain, such as that of the hydrocarbon chain between the two functional groups, is at least sufficient to produce a polyamine with or without water-dispersible chain extended fatty acid moieties. It should be, and preferably should be a polyamine with or without water soluble or emulsifiable chain extended fatty acid moieties.

One type of suitable example of a bifunctional organic compound for molecular growth is oxalic acid, malonic acid, succinic acid,
Includes glutaric acid, adipic acid, and pimelic acid. These materials consist of well known classes of acids, and their methods of preparation are well known to those skilled in the art. Halogenated derivatives of dicarboxylic acids or their anhydrides or esters of their acids can also be used as chain extenders. In addition, these types of chain extenders can be used as a component of a mixture with polyamines to form polyamine I as a condensation reaction to form polyamine I.

The bifunctional organic chain extenders can be used alone or in a mixture of chain extenders. Saturated carboxylic acids are preferred,
Small amounts of unsaturated dicarboxylic acids such as maleic acid and the like can be used as a mixture with saturated dicarboxylic acids. It is most preferred to use an ester structure such as a dialkylsuccinic acid, eg diethylsuccinic acid.

The reaction conditions for polyalkylene polyamines and reaction products of polyalkylene imines and polyamines with fatty acid materials (described below), and polyamines containing difunctional organic chain extenders depend on the extent of the particular compound used ( dgree). In general, the reaction is one in which the chain extender is not in excess, but if there is no chain extender at all, a significant proportion of the reaction is possible. For example,
When the chain extender is a diester, the temperature is about 80 ° C.
It can be about 180 ° C., while in diepoxy compounds the temperature can be used at room temperature or even around room temperature, while the diacid chain extender is from about 180 ° C. to about 220 ° C.
Can have high temperatures. The time of all these reactions can be varied to suit a specific temperature within the indicated range,
Generally, at least a time, a fatty acid material dispersible in water,
Depending on the starting reaction components, the chain-extended polyamine with or without is sufficient to give a satisfactory yield. Preferably, the reaction is carried out in the pure state if the reaction components and the reaction products have a suitable viscosity. If the viscosity of one or more of the reaction components or reaction products is too high for the suitable reaction conditions, the viscosity can be increased by heating or
Alternatively, it can be lowered by using a solvent of more than that. When the diepoxy contains a usable alcohol or alcohol ether, the reaction is usually carried out in the pure state even though the diester is used together.

The above-mentioned types of polyamines or polyamines, including chain-extended polyamines, including polyalkylene polyamines, and difunctional organic compounds, although not limiting to the scope of the invention, are reacted with one or more fatty acid materials. It is considered to be partially aminated via

Suitable non-exclusive examples of these fatty acid materials include fatty acids, fatty acid esters, fatty acid halides or anhydrides of their acids, where the major amounts of these fatty acid materials form condensation products. In order to react with chain-extended polyamines or polyamines to form condensation reaction products,
Value. The fatty acid materials may be essentially saturated and preferably they are aliphatic ethers, which are linear or of varying branching, which are described here and in the claims as fatty acid materials. Fatty acids having 1 to about 22 carbon atoms, preferably 7 to 12 carbon atoms are preferred. Suitable non-exclusive examples of fatty acid materials include acetic acid, pelargonic acid, 2-ethylhexenoic acid, isononanoic acid, oleic acid, undecenyl acid.
enic), caproic acid, caprylic acid, octanoic acid, capric acid, lauric acid, and stearic acid. Esters, acid halides, and anhydrides of these acids as described above may also be used. When fatty acids having 6 or less carbon atoms are used, as a mixture with fatty acids having more than 6 carbon atoms, and in small amounts not exceeding about 50% by weight of the mixture of fatty acids on a weight percent basis. Should be used in a mixture.

The various components of any mixture can be used in other types of mixtures, but the fatty acids and / or esters and / or acid halides and / or anhydrides can also be used in various types of mixtures. All mixtures have acid halides such as fatty acids and / or acid chlorides and / or esters and / or anhydrides as the main amount of the mixture. Some of such mixtures contain minor amounts of difunctional and / or trifunctional fatty acids and / or polymeric fat acids and / or fat acids. Polymer fat acid is a polymerized fat acid, either in dimer, trimer, or higher polymerized form, and such is the major proportion of acid dimer, small amount of It consists of a polymerization mixture of trimers and more highly polymerized forms, and acids with some residual monomer. Fat acid is a natural and synthetic monobasic aliphatic acid having a carbon-hydrogen chain of 8 to 24 carbon atoms, including ethylenically unsaturated and acetylenically unsaturated acids. Another type comprises a mixture of saturated and unsaturated fatty acid materials with a small amount of unsaturated fatty acid material, and
Acid mixtures such as those obtained by hydrolysis of natural fats and oils are useful. Suitable examples of these are coconut oil, corn oil, cottonseed oil, tallow, tall oil, and soybean oil. Acids prepared from these fats and oils are about 14
Various mixtures of .about.20 carbon atoms, some of which are, for example, tetradecane, tetradecene, hexadecane, hexadecene, octadecane, octadecene,
It includes both saturated and unsaturated fatty acids including eicosanoic acid, decanoic acid, dodecanoic acid and octadecatrienoic acid. Although straight chain or branched chain fatty acids can be employed, these materials are primarily useful in admixture with saturated fatty acids. Such widely varying fatty acid material can be adopted, but as a fatty acid material, 2
Functional and trifunctional fatty acid and / or unsaturated fatty acid materials are generally employed in as little as 50% by weight or less of the mixture.

In general, any reaction of the above fatty acid materials with polyamines and / or chain extended polyamines can occur to some extent depending on the particular reaction components.
For example, when the polyamine is a polyalkylene polyamine, the reaction components may cause the reaction at a temperature ranging from room temperature to high temperature. For example, for a fatty acid material that is a halide type, the temperature may be from room temperature to about 70 ° C., while for a fatty acid material that is a fatty acid type, the temperature is preferably from about 140 ° C. to about 200 ° C. or It can be even higher, while in the absence of any solvent fatty acid materials, which are preferably diesters such as succinic acid, are in the range of about 130 ° C to about 100 ° C. When the fatty acid material is a fatty acid and lower reaction temperatures are employed, usually 1 mole of condensed water is removed for each 1 mole of reacted acid, while higher reaction temperatures are used. An additional mole number of water can be removed from the. For esters as fatty acid materials, usually 1 mole of alcohol can be removed at the lower temperature and 1 mole of water at the higher reaction temperature. The molar ratio of the amounts of the two or three above-mentioned reaction components for producing the polyamine I is in the range of 1 to 4 polyamines for organic compounds and about 1 to 1 polyamines for fatty acid materials. About 1
It can be a bifunctional organic compound that is 0 and / or a polyamine for fatty acid materials. Preferably, the molar ratio is in the range of about 1 for organic chain growth agents, in the range of about 1.005-2 for polyamines, and about 0.25-about for fatty acid materials. 25. Most preferably, the molar ratio of chain extender to polyamine is from about 1
It is 1.25.

Any polyamine I material is reacted with one or more amine-reactive silanes to form the silylated RP polymers of this invention. Does the organofunctional alkoxysilane or its hydrolysis product have two or three reactive moieties on the organofunctional portion of the compound capable of reacting with the amine portion of polyamine I by using the term amination reactive silane? Or it means that you can have. The term is meant to include organofunctional alkoxysilanes that are capable of reacting with Polyamine I through a material that is not essentially amine-reactive, but which aids the reaction. For example, an aminoorganofunctional alkoxysilane can react with a dialdehyde or diacid to give an amine-reactive silane. On the contrary, it is possible that after reacting the reactive amine of polyamine I with a dialdehyde or diacid, a silane that is not amine reactive may react with polyamine I. Non-exclusive examples of suitable amine-reactive silanes are given below for each of the above types, and each compound may also be used in its hydrolyzed or partially hydrolyzed form. These forms include the silanol and / or polysiloxane equivalents. The latter exists only to the extent that gelation of the silane material and precipitation from solution can be avoided.

For the epoxy-organofunctional silane ester, the structural formula is CH ₂ CH (O) -CH ₂ -O- (CH ₂ ) _x -Si.
Can have (OR) ₃ , x is an integer from 1 to 6, and R is, for example,
Methyl, ethyl, propyl, lower alkyl such as isopropyl, or structural formula: a _{CH 2 CH (O) -C- (} CH 2) z -Si (OR) 3 Mochie, z is an integer from 1 to 6 Some are useful.
Suitable non-exclusive examples of epoxysilanes include γ-glycidoxyalkyltrialkoxysilanes, where the alkoxy groups can be methoxy or ethoxy, δ-glycidoxybutyltrimethoxysilane and β-glycidoxyethyltriethoxysilane. Silane is included.

Non-exclusive examples of isocyanate silanes for isocyanate organofunctional silane esters include:
γ-isocyanatopropyltriethoxysilane, also known as silane under the name CAS, 3-
(Isocyanate) propyl-triethoxy is included. This silane is trade name Silane Y-9030 (Sila
ne Y-9030) as Union Carbide Company (U
is an organofunctional silane commercially available from Nion Carbide Corporation. This substance has a chemical structural formula of O = C = N (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ , is a transparent liquid with an active substance of 95% or more, and has a specific gravity of 25 ° C / 25 ° C. At 0.99
And has a refractive index (nD) of 1.419 at 25 ° C., from water white to light amber color.
And can be diluted with hydrocarbons, ketones, ethers, amides, or esters and is soluble in benzene, toluene, hexane, acetone, diethylcarbitol, dimethylformamide, cellulose acetate.

A preferred example of the acryloxy group-containing organofunctional silane ester is γ-methacryloxypropyltrimethoxysilane available under the trade name A-174 from Union Carbide and Chemical Company, and other γ-acryloxy Acrylate alkylalkoxysilanes such as propyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyltris (2-
Methacrylate alkylalkoxysilanes such as (ethoxyethoxy) silane and the like are included.

The molar ratio of polyamine I to amine-reactive silane can range from about 0.1 to 25 amine-reactive silane to about 1 polyamine I, most preferably 1 to 0.5. It is about 1 to 1. Excessive excesses of amine-reactive silanes result in lesser improvement in the use of textiles as coating agents. Preferably, an amino-reactive silane with a molar ratio of about 1 is allowed for every 2500 polyamine I molecular weights.

In the preparation of the silylated RP polymer, the amine-reactive silane and the residual amine number of about 200 to about 800, and the residual acid number of about 20 and partially amidated or acylated. Reaction with the polyamine, polyamine I, is preferred. In general, the silylated RP polymer can be prepared by combining the reactants either sequentially or simultaneously with stirring at a suitable reaction temperature for a period of time and with stirring. Since both reaction components are preferably liquid, the reaction can be carried out in a pure state (solvent-free state). If the particular Polyamine I has a viscosity that is too high for proper agitation, the Polyamine I can be heated to reduce the viscosity or diluted with a suitable solvent. Such solvents include methanol, ethanol, lower alkyl alcohols such as isopropanol, polyethylene glycol, polypropylene glycol, and mixtures thereof and copolymers of said glycols, and ethoxylated alcohols such as ethoxylated lower alkyl alcohols which are liquid, And water. When a solvent is used, it is preferred to combine Polyamine I with the solvent followed by addition of the amine-reactive silane. In both solvent-free and solvent-prepared systems, the amine-reactive silane is preferably added slowly with stirring over about 10 to 50 minutes. As mentioned in the description of the particular reaction components above, the temperature of the reaction may vary depending on the particular type of reaction components. The reaction is preferably performed so that most of the silane added will react if not all. After the silane is added, stirring of the mixture is continued at the same temperature as the silane was added. Generally, a time of about 15 minutes to 8 hours can be employed. Polyamine I larger than about 1: 1
The use of a molar ratio of amine-reactive silane to: may result in reduced properties for certain substrates coated with silylated RP polymer. For example, in the heat cleaning of fabrics, especially those made of fiberglass strand yarns, it is industrially necessary to remove most, if not all, chemical treating agents from strands or strands that have no deposits or residues on the fabric. is there. If the amount of amine-reactive silane is too high compared to polyamine I, then such a precipitate will probably form. After formation of the silylated RP polymer, either without solvent or with solvent, the silylated RP is formed.
The polymer is diluted with water to give a formulation that is mostly water. If the aqueous solution of silylated RP polymer has a pH that is too high, such as 11 or higher, an acid, preferably an organic acid such as acetic acid, can be added to bring the pH to a low level.

In addition to the silylated RP polymer and water, other ingredients can be added to form a suitable coating formulation. Any other ingredient known to one of ordinary skill in the art may be used. For example, silylated RP polymers having lubricious properties may be used alone or in coating formulations with other components to treat substrates having oxide surfaces such as glass. Suitable substrates include glass fibers formed into fibers of any diameter made from a glass melt stream of any glass composition known to those skilled in the art. For example, suitable compositions include "621 glass" and "E glass", "S glass", "D glass", and similar glass compositions free of or reduced amounts of boron and / or fluorine atoms. included. Preferably, for the treatment of these substrates, the formulation preferably comprises a silylated RP with the addition of one or more film-forming polymeric materials and / or additional lubricants and / or processing aids and mixtures thereof. It is an aqueous polymer formulation.
The silylated RP polymer is particularly suitable for use with other compounds to provide starch lubricated type sizes for glass fibers, fabrics, strands and / or yarns. These materials include starch lubricants for textiles as coating agents for fibers, starches for water-based sizing agents and binders, lubricants such as oils and waxes, emulsifiers and / or surface active agents for oils and / or waxes. The lubricating properties of the silylated RP polymer, which may include an agent and water, are also polyester,
It may also be useful in treating organic fibers such as polyaramid. In formulations for the treatment of glass fibers, the non-aqueous components include silylated RP polymer lubricants, and the solids range for those components is generally about 1-30% by weight of the aqueous formulation with excess water. .

Today, the industry requires glass fiber woven strands to reduce filament breakage during use in weaving, reduce the allowable insertion time of the strands in high speed rooms, especially new air jet looms, and in good condition. A strand having heat cleaning ability is required. The new air jet loom operates at a much faster speed than the old conventional shuttle loom. In addition, the heat cleaning process of producing conventional finished fabric products can result in significant loss in strength properties from that of unheated fabrics. Silylated RP that provides both cationic lubricity properties and the mechanism of a silane coupling agent
The use of polymers can turn standard starch oil sizes for fiberglass fabrics into better performing products with improved heat clean properties. This improvement may allow the heat-cleaned fabric to maintain greater strength than the pre-heat-cleaned strength while maintaining good weaving and heat-cleaning properties. When a silylated RP polymer, which is preferably a silylated amidated polyamine, is used with the preferred starch oil size, the glass fiber fabric has good strength properties, low filament breaks during weaving, and good heat cleaning properties. The preferred starch oil size is aqueous based and has a controlled amount of at least one starch and a particular type of oil with the preferred silylated polyamine and a non-starch second film forming polymer starch oil size. Is. Alternatively, the water soluble starch can be used with the oil without the presence of the non-starch second film forming polymer.

In the following description of the textile strands of the present invention, "wt%" with respect to the components of the binder refers to the wt% of the non-aqueous components of the binder. This includes the solids content of emulsions and dispersions, whether they are aqueous-based and non-aqueous liquid and solid materials. This is an annotation when the term "weight percent" is used in different contexts.

Suitable examples of starch lubricant sizes, including starch oil sizes in general, can be any of those known to those skilled in the art, such as "The Manufactu".
ring Technology of Contin
uous Glass Fibers "(KL Lo
werstein, Elsevier Publish
ing Company, New York, 197
3, Page 192-193).
The authors generally state that typical starch oil sizes have been utilized today in the preparation of glass fiber strands for textiles. Other starch oil sizes include U.S. Pat. Nos. 3,227,192 and 3,265,5.
No. 16 and No. 4,002,445 are included.

Typically, the types of starch that can be used include those having a low amylol content, which is up to about 40% by weight of the starch composition, preferably about 1%.
It means that between 0 and about 30% by weight of amylose can be contained in the starch. A preferred starch is a mixture of modified potato and cross-linked corn starch, both of which have a low amylose content. A starch that meets these indices is Amaizo 213, which is American Maids Products.
an Maize Products Compan
Y) Starch and National 15 manufactured by
54 (National 1554) as National Starch Com
There are starches manufactured by Pany). Another example of a suitable starch is Avebe.
e b. a. ) 9607 PT Foxhol. A low amylose starch that is water soluble after cooking, such as potato starch ether, which is non-ionic, such as that available under the trademark "Kollotex 1250" from the Netherlands. The amount of starch provides an effective amount of film former for the textile strands of the present invention, or when or with the aid of a second film former. By "effective amount" is meant an amount of film former sufficient to properly pack the individual glass fiber filaments together and maintain the integrity of the strand bundle during processing.

Any lubricant known to a person of ordinary skill in the art may be used in the amount conventionally or traditionally used and includes, for example, cottonseed oil, corn oil, soybean oil, glycerol trioleate and the like. Another lubricant that may be used includes fatty acid esters of non-polymeric polyhydric alcohols such as triols. A non-exclusive example is Kesco oil (Kessco oil, such as trimethylolpropane triester).
oils), or pentaerythritol tetraester, wherein the alkyl group of the ester is from about 7 to about 10
Can have 4 carbon atoms. These materials are either liquid or solid at room temperature, ie about 18-23 ° C., but preferably nonionic oils such as hydrogenated oils such as vegetable oils are used. The amount of nonionic lubricant present can be used in any amount known to those skilled in the art. The amount is from zero to more than 25, preferably more than 27 (% by weight). Most preferably, the amount is no more than an amount that results in a decrease in the stiffness of the strand when it is withdrawn from the strand package. Also, amounts in excess of this can adversely affect the spinnability of the sized fibers into textile yarns. The ratio of the amount of oil to the amount of starch is most preferably greater than 5/12 or 0.4, and generally up to about 1.5. A suitable hydrogenated vegetable oil, and preferred is hydrogenated soybean oil, Eclipse 102 (Eclipse 1).
02).

In preparing a dispersion and / or emulsion of a lubricant having limited water solubility, any of the typical emulsifiers and / or surfactants, in combination with conventional amounts, in relation to the starch lubricant size. But it can be used. Non-exclusive examples include US Pat. No. 3,227,19
No. 2, No. 4,681,805, and No. 4,197,
No. 349 includes those disclosed in each specification. A typical emulsifier is octylphenoxypoly (ethyleneoxy)
Igepal CA-630 (Ig
such as epal CA-630). Another exemplary and suitable material is octylphenoxypolyethoxyethanol, Rohm and Haas Company (Ro
HM and Haas Company) Triton X-100 (Triton X-100).
In a preferred embodiment of the invention, Tween 81 (T
A single emulsifier such as ween 81) may be used or Igepal CA-630 (Igepal CA).
-630) and Triton X-100 (Triton X)
A mixture with -100) is employed in equal weight.

Any conventional wetting agent will be suitable for the practice of the present invention, so long as the emulsifying agent or wetting agent used has a suitable hydrophilic and lipophilic balance in the emulsion. Generally, when the above combinations are employed, each emulsifier is about 1 to about 5% by weight solids, preferably about 1.8 to 4.5% by weight. In all cases, the total amount of emulsifier used is typically between 3 and 9% by weight (solids).

Suitable oil-in-water dispersions or emulsions are generally prepared using one or more oil lubricants and one or more emulsifiers as described above. To maintain the stability of the dispersion or emulsion at the preferred starch oil size, on a solids basis,
The weight percentage of all starch components is preferably 5
Care is taken to ensure that it is below 0%, most preferably below about 45% and above 35% by weight. Similarly, the oil lubricant utilized preferably has a ratio of oil quantity to starch of less than 1,
25-40%, and most preferably 27-38%
Given in.

The presence of the non-starch second film-forming polymer enhances the ability of the filaments or fibers to stick together together at various locations along the fibers of the starch provided with an effective amount of film-forming agent. To assist. This second film-forming polymer may be present in the preferred starch oil size within the range of about 0-20% by weight of the non-aqueous component of the binder. Such materials are
Poly (vinylpyrrolidone) (“PVP”) homopolymers and copolymers of PVP, poly (vinyl acetate), and poly (vinyl alcohol), epoxy resins, polyesters and the like. An alternative to PVP is low molecular weight polyvinyl acetate as it provides a flexible film on the surface of the glass fiber bundles. Generally, the second film forming agent is present in an effective amount with the starch to provide effective strand coverage and integrity, such as bundling, so that the filaments are bundled into strands and then the bundles become dense. (Compactness) and maintains integrity as the strands are dried and on subsequent strokes. The preferred amount is in the range of about 3 to 15% by weight so that one or more starches always constitute a good film-forming material in the binder. When the material is PVP, and when the amount is greater than about 5% by weight, the amount of oil lubricant is less than 40% by weight and preferably less than 35% by weight. In other words, an amount of PVP greater than 5% by weight results in a concomitant reduction in the amount of oil lubricant of less than 40% or less than 35% by weight. Most preferred this reduction corresponds one-to-one. The most preferred effective film former amount used for this purpose is, for example, in the range 3-8% PVP.

Although any of the aforementioned silylated RP polymers can be used in starch oil size, preferably PP
Trademark Alblaspin 227 (Alubras) from Company G
a silylated amidated polyamine available as pin 227). Generally, the amount will be in the range of from about 0.5 to about 15% by weight, preferably from about 1 to about 4% by weight (solids content of size). Preferably, using a silylated RP polymer having both a desired degree of silylated and a desired amount of fatty acid moieties for lubrication reduces the need for the use of any organosilane coupling agent and / or cationic lubricant or remove. This is a result of the use of the silane coupling agent through the silylated RP polymer being more effective than the individual use of the organosilane coupling agent. The preferred starch oil size is essentially free of any additional monomeric silane coupling agent. However, the organosilane coupling agent and the cationic lubricant material may be used in equal or lesser amounts with the silylated RP polymer, due to the presence of the silylated RP polymer from those used in known starch oil sizes. The amount of coupling agent and cationic lubricant can be reduced. Coupling agents and / or cationic lubricants are also silylated R
It may be present when the P-polymer has a low amount of silylation or a low amount of lubricious groups. In the preferred starch oil size, the silylated RP polymer is present in a solution or mixture pH adjusted and the silyl moieties are partially and / or fully hydrolyzed. Any acid suitable for the hydrolysis of silane coupling agents known to those skilled in the art can be used. Preferably acetic acid is used in an amount for at least partial hydrolysis of the hydrolysable part of the silyl groups of the silylated polyamine.

If it is desired to use an additional amount of organosilane coupling agent or cationic lubricant, then anything known to those skilled in the art may be used. Non-exclusive examples include mono-, di- or poly-aminosilanes such as γ-aminopropyltriethoxysilane as coupling agents; vinylsilanes and glycidolpropyltrimethoxysilane and the like, and polyalkylenepentas as cationic lubricants. Alkylamine imidazoline reaction products of amines with stearic acid and amidated polyamine lubricants. As a non-exclusive example of the former,
Rhone-Poulen sold under the trade name Cation X
c, Inc. ), Lyndall / North Div
ision, palton, georgia 3072
There are 0 materials, however, they are preferred in that they limit the use of cationic materials. A suitable example of the latter is C
Partially amidated polyalkyleneimines such as the reaction product of a mixture of ₁₂ to about C ₁₈ fatty acids and polyethyleneamine having a molecular weight of about 1200, which are disclosed in US Pat. No. 3,579,265. Has been done. Examples of these commercially available products include Emery Industries Cincin.
Trademark Emery 6717 (Em manufactured by Nati, Ohio
ery 6717) and Emery 6760, which is a 65% version of the 6717 material. The lubricant may be used in an amount based on weight percent of the non-aqueous components of the binder of more than 1 and up to about 6, preferably 1.5 to 4.

Any natural and / or synthetic wax known to those skilled in the art may be used as an optional ingredient, either in the preferred starch oil size or in any starch oil size. A preferred amount may range up to 25% by weight. An example of a suitable wax is US Pat. No. 4,795,678 to Girgis.
Those listed in the specification can be cited. When the amount is greater than 0, there can be a concomitant decrease in the amount of starch for any increase in the amount of wax, as low as 65% by weight. Preferably, the wax is because the oil lubricant is the only nonionic lubricant present in the binder.
The wax should not be present in the binder. The amounts of starch and oil present in the binder are at least 35 and at least 25, respectively, based on the weight percent of the non-aqueous components of the aqueous based binder. For these starch and oil amounts, the oil to starch amount ratio may be at least greater than 0.4. And can be as large as 1.5. Specific types of oils are hydrogenated dietary oils and / or mineral oils and / or fatty acid esters of non-polymeric polyhydric alcohols.

Representative fungicides are also employed in the starch oil sizes of this invention to prevent blue mold, mildew and / or fungi from attacking the amylose-containing starch derivative. Therefore, there may be an effective amount of fungicide as would be known to one of ordinary skill in the art as in the following non-exclusive examples.

As an example of the above, Chemtreat (Che
Chemtreat Cl-2141)
(Chemtreat C1-2141), tributyltin oxide manufactured under the trade names of Biomet 66 and methylenebisthiocyanate are typical metal-containing compounds that can be used, and M & T Chemical Co. T Chemical
al Co. , Inc. There are organometallic type materials such as bis (tri-n-butyltin) oxide and n-alkyldimethylbenzylammonium chloride which are manufactured by

Water is usually the carrier of solid and / or non-aqueous ingredients in size. The amount of water present in the size is such that it is suitable and easily applied to the glass fibers during their formation. The amount of water for this purpose gives the binders a viscosity which is sufficient for application of the binder and formation of strands to the fibers during their formation. Generally, this viscosity is consistent with a total solids (non-aqueous) content of aqueous size that is in the range of about 0.5 to about 30% by weight, preferably about 3 to about 10% by weight. The total solids should be adjusted so that the size level is compatible with the glass fiber application. For example, with excess water size, the viscosity is between about 3 and about 50 centipoise (measured at 20 ° C). Thickeners can be used to increase the viscosity of size, but generally if the viscosity is 100 centipoise (20 ° C.
Or more), the size is difficult to apply to the glass fiber while it is being formed.
The strands have a size that upon drying reduces the moisture content of the size to an amount of from about 0.3 to about 3% by weight of the strand to form the glass fiber woven strands of the present invention. These strands can generally provide a reduction in filament break of up to 90% over some available glass fabric strands.

Such an improvement is directed to the textile strands in terms of twistability, weavability, heat cleanability, and slashing compatibility.
lit) maintenance and in some cases even improvements. One of the improvements is observed in the heat clean properties for glass fiber fabrics with a starch oil sizing composition having a separate monomeric silane coupling agent.

In general, size may be prepared by the simultaneous or sequential addition of size-forming components. One suitable continuous addition embodiment is a starch or starch mixture, in which the individual components have not already been added to each other, an oil lubricant or oil lubricant mixture in the form of an emulsion, a non-starch film-forming polymer, a cationic Lubricant, organoalkoxysilane,
And a fungicide and a balance amount of water are present to obtain the desired amount and solids level for the binder. In a preferred continuous addition embodiment, at least one starch and water-soluble ingredients are mixed and oil-soluble ingredients are added.

The aqueous binders are preferably applied to the glass fibers during their formation by any method known to those skilled in the art. Application of the binder to the fibers results in fiber strands that can have a size of from about 0.5 to about 3% by weight, and preferably from about 0.8 to about 3% by weight on a loss on ignition (LOI) basis. The LOI test is a well known technique for determining the amount of glass fiber size.
The diameter of the filaments or fibers generally ranges from less than 3 μm to as much as 30 μm, such as from beta fibers to fibers with larger diameters to twisting of bundles of fibers. The glass fibers themselves can be formed by any method known to one of ordinary skill in the art by forming fibers from direct or indirect melt process and bushing orifices. Preferably, water spray and conditioned air are used for cooling the fibers, and the fibers are preferably treated with an aqueous size immediately after bushings and their cooling. The fibers are drawn from the bushing by a winder, and then size is applied, the fibers are bundled into one or more strands, and wound into an annulus on a winder.

Within a multi-layered package, the glass fiber strands will typically have a moisture content in the dry package of about 1-15.
Reduce to within the wt% (of package weight) range.
Achieving a reduction in moisture content is usually accomplished by drying the package in an oven at conventional temperatures and times, or by air drying for a conventional period of time. Another drying technique involves stacking the strands on a paper tube and keeping them under that condition for 8 hours under humidity and temperature control. The strands are twisted and wound on a bobbin. Conditioning and air drying during twisting provides a dried residue of binder on the filament surface, forming a unitary strand.

Strands of glass fibers having a twistable binder of the present invention may be twisted by any glass fiber twisting technique known to those skilled in the art. For example, any twist frame for twisting glass fibers known to those skilled in the art is useful for twisting the glass fibers of the present invention. For example, the twist is "The Manufacturing Technology.
noology of continuous glass
s Fibers "(K. L. Lowenstein,
Elsevier Publishing Compa
ny, New York, 1973, the seco
ed edition 198). In general, the level of twist can range from about 0.5 to about 3 (turns / inch). Twisting yarns have the requirement that twistable strands must be flexible enough to allow the strands to be precisely twisted and to allow individual filaments to move freely within the bundle or strand. Twisted strands or yarns on bobbins are useful in the manufacture of reinforced and composite materials for woven and nonwoven fabrics, knit and / or braid products and various tape products. The woven fabric may be manufactured in a conventional shuttle room, an air jet room, a rapier room, or a shuttleless loom known to those skilled in the art.

For a more complete understanding of the invention, a method of preparing a silylated RP polymer which is a lubricant according to the invention and which may be used alone or together with another component for coating a substrate. Examples are provided below and showing how to prepare coating formulations used to prepare treated strands.

Example 1 804.4 g of polyethyleneimine having a molecular weight of about 1200
A nitrogen inlet / outlet, a thermometer, a thermowatch (Thermo
watch. Trademark) temperature regulator, heating mantle,
A 3 liter reaction flask equipped with a water condenser, Barrett ™ water trap and a Teflon paddle stirrer was charged. To this, enanthic acid (33%), pelargonic acid (27%), caproic acid (26%), octanoic acid (9%)
%) And valeric acid (5%), 343.3 g of a carboxylic acid mixture was added along with 235.8 g of acetic acid. The reaction flask was briefly flushed with nitrogen for about 5-10 minutes, then the nitrogen feed was stopped and the mixture was stirred. Finally the two phases were mixed, slightly darkened and self-heated to 100 ° C. When the exotherm was over, external heating was started. Temperature is about 1
Upon reaching 58 ° C., the reaction formed water, which began to distill and was collected in the trap. The reaction mixture was gradually heated to about 200 ° C. over about 1 hour and water was removed periodically when the trap was full. The amount of water produced was finally 123.9 g, but the expected theoretical amount was 11
It was 7.9 g. There was also a small amount of organic phase, which was later separated. After 6 hours at 200 ° C., a nitrogen purge was started and the reaction mixture was cooled. 123 products recovered
With a weight of 5.5 g, this corresponded to a yield of 97.6%. This product is a polyethyleneimine polyamide and has a polyamine I product of 4.65 mg KOH / g.
It had an average acid number of and an average amine number of 395 mg KOH / g.

Several variants of this polyamine I were obtained in a similar manner. Table 1 shows their characteristics.

[0073]

[Table 1]

The ratio of X: Y: Z is the ratio of monomers in the polymer, where X is the unacylated species (C ₂ H ₄ N
H), Y is an acylated species (C ₂ H ₄ NCOCH
₃ ) and Z are long chain acylated species (C ₂ H ₄
NCOR), where R can be a straight chain with an average chain length of about 6-7. The range of X: Y: Z ratio is about 0.5.
3 to 0.54: 0.18 to 0.27: 0.19 to 0.3
It became 2.

A 1 liter reaction flask equipped with a nitrogen inlet / outlet, a thermometer, a Thermowatch ™ temperature regulator, a heating mantle, a Teflon® paddle stirrer and a dropping funnel had a residual amine value of about 400 mg KO.
Polyamine I Product 4 of Example 1 up to H / gm
59.2g was charged, and the average water content was 271mg /
dried with molecular sieves up to kg 272.
9 g of polyethylene glycol 300 was charged to the reaction flask. The dropping funnel was charged with 48.6 g of gammaglycidoxypropyltrimethoxysilane and finally 4
7.8g was added. The mixture of polyamine I and amine-reactive silane was stirred under nitrogen and heated at 70 ° C. The nitrogen feed was stopped when the silane addition over 47 minutes under stirring was begun. After the addition, the mixture was stirred for an additional 2.5 hours at 70 ° C. The reaction mixture was filtered while hot with a dry pressure filter equipped with a glass fiber filter and collected in a dry bottle. The amount of final product was 736.9 g, which corresponds to a yield of 94.5%. The final product is viscous and contains 61.4 g
Diluted with polyethylene glycol 300. 1 more
59.7 g of polyethylene glycol 300 was added for dilution and the mixture was heated to 60 ° C. and mixed. Final product averages 98.5% solids, amine number 184, pH 10.7 and density 1.08 in 4% aqueous solution diluted in water.
Had.

Example 2 Method for producing silane-modified TEPA type polyamine I Material Weight Mol Tetraethylene pentamine (TEPA) 490 g 2.59 (manufactured by Union Carbide) Diethyl succinate 361 g 2.07 (manufactured by Eastman Kodak) Octanoic acid 149 g 1.03 (manufactured by Eastman Kodak) Methanol 795 g- (manufactured by Fisher) Epoxy-functional silane (A-187) 123 g 0.52 (manufactured by Union Carbide) TEPA, heating mantle, air stirrer, A 2 liter reaction kettle equipped with a distillate collector, thermometer and nitrogen inlet was charged, diethyl succinate was added to the reactor and a nitrogen purge was started. The mixture was heated with stirring.
When the reaction temperature reached 140 ° C., a condensate of ethanol first started to form. When ethanol production was nearing completion, the temperature was raised to 160 ° C. Heating continued until no condensate formed (about 1 hour). During this time, 18 in total
6.5 g of distillate was collected. Then the temperature is 120 ℃
And added octanoic acid. Then set the temperature to 200
C. and held at that temperature for 1.5 hours, during which 18.
2 g of distillate was collected. Lower the temperature to 55 ° C, 79
5 g of methanol solvent was added, at which point the nitrogen purge was discontinued.

The mixture is cooled to room temperature and stirred with A-
187 was added. The mixture was then stirred for 1 hour at room temperature.

Another example of silylated RP polymer is also Example 1.
And a procedure similar to 2. Details are shown in Table 2.

[0079]

[Table 2]

In Example 3, versamide was charged to a reactor equipped with a nitrogen inlet, an addition funnel, a mechanical stirrer and a condenser, and the reactor was heated to 50 ° C. The solvent methanol was added with stirring, then silane was added slowly from the addition funnel at 50 ° C. with stirring and held for about 8 hours. 11.7 g of the reaction product was added to 298 g of distilled water with stirring to make the reaction product a solution.

In Example 5 and similarly Example 7,
The combinations of Emery 6717 and the silanes shown in Table 2 are
The reaction was carried out in a pure state because it was all liquid. The temperature of the mixture was raised to about 70 ° C. to reduce the viscosity of the mixture.

In Example 6, Emery 6717 was placed in a beaker and dissolved in isopropyl alcohol with stirring to warm the mixture. Then cool the solution to room temperature,
When the maximum temperature of 34 ° C. was reached with stirring, the silane was added slowly. Again, the reaction product was diluted with ethanol to 50% solids to increase storage stability and / or ease of handling.

In Example 8, the infrared spectrum of the reaction mixture demonstrates acryloxyalkylsilane modification of Emery 6717. Although the reaction is a reversible reaction, the equilibrium may change so that the acryloxyalkylsilane A174 silane, at high concentrations or in acidic conditions, aids in the formation of silylation. The effect of acidity is pH 3, 5 and 9
In the infrared spectrum of an aqueous mixture of A174 and Emery 6717 in.

The absorbance at about 1700 cm ^-1 is A17.
4 carbon double bond oxygen stretch

[0085]

Embedded image

Due to At pH 9, the absorbance was highest, indicating little or no reaction between A174 and Emery 6717. As the pH decreases to 5 and 3 by hydrochloric acid, the silylation reaction is assisted and the peak of carbon double bond and oxygen bond is increased.

[0087]

[Chemical 9]

Becomes low and shifts to the low frequency side.

In Example 9, the solvent was water containing 36 g of acetic acid, and 1000 ml was used as a modification method in the aqueous phase.
A first solution was prepared by weighing 500 g of 60 ° C. distilled water having a pH of 6.5 in a plastic beaker. Emery 6717 was added with stirring at 20 ° C. and stirring was continued until a viscous solution was formed. The second solution was prepared by measuring distilled water having a pH of 6.5 at 20 ° C. in a 500 ml plastic beaker and adding acetic acid. Silane was added with stirring and stirring continued until the solution became clear. Then, with stirring, the first solution and the second solution
Solution was added at a rate of about 5 ml per minute. All solutions were added and stirring continued at about 60 ° C. for an additional hour.

In Table 3, starch-oil sizing (s
Figure 3 shows a silylated RP polymer combined with additional components to obtain three formulations that can be useful as a touch-oil sizing composition. These sizes were prepared by essentially the same method described below for similar components of size.

A 60 gallon starch-oil size dispersion (228 liters) was prepared by the following method.

(A) A slurry tank was charged with water in an amount of about 35% to about 40% by weight of the total size, to which the amount of National 1554 Starch and Amaizo 213 shown in Table 3 was added. Add starch. These components are preferably 255F ± 5 ° F
Cook at (124 ° C ± 3 ° C) for about 1 minute with a jet cooker at a circulation rate of 1.95 gallons (7.41 liters) per minute. Pump cooked starch into the main mixing tank.

(B) In another mixing tank, cold water was added in an amount of about 3-4% of the total size, to which the amount of glacial acetic acid shown in Table 3 was added under slow stirring. Then the silylated RP polymer of Example 1 is added in the amount shown in Table 3 and the mixture is slowly stirred until the solution becomes clear. Transfer this mixture to the main mixing tank.

(C) Another mixing tank was charged with hot water in an amount of about 3 to 6% of the total weight of the size, and the amount of PVP K-30 (polyvinylpyrrolidone film forming agent (GAF) shown in Table 3 was added thereto. Chemical Co., Ltd.)) is added. PVP
PVP K until K-30 dissolves and the solution becomes clear
Stir vigorously with -30 to disperse in water. The obtained liquid is transferred to the main mixing tank.

(D) A specific oil in the amount shown in Table 3 is placed in an Eppenbach mixing tank together with one or more emulsifiers in the amounts shown in Table 3. Start the Eppenbach mixing tank and heat to a preferred temperature of about 100 ° F to 140 ° F (about 38 ° C to 60 ° C). Mix all ingredients well and first mix about 5% of the total amount of 140 ° F to 160 ° F (60 ° C to 71 ° F).
℃) warm water, the mixture turns white (inverter)
Add slowly until t). The resulting mixture is then transferred to the main mixing tank.

(E) All components in the main mixing tank are
Dilute with water to a final volume of 60 gallons (228 liters) at a temperature of about 145 ° F ± 5 ° F (about 63 ° C ± 3 ° C).

The size thus produced was pumped from the main mixing tank using a conventional glass fiber forming apparatus through a suitable tube to the glass fiber forming level where the fiber glass forming bushing was located. For the bushing, an 800-chip 2G-75 bushing having a belt applicator provided with a sump arranged at the bottom can be used. A rubber belt attached to the roller is passed by the roller through the sump in the applicator to pick up the size of the applicator surface. 8
The glass fiber or filament drawn from the 00 chip bushing can be passed over and in contact with the surface of the rubber belt applicator, the size on the belt surface being applied to the filament when the filament is drawn to the upper size. It The filaments can be collected in strands in a gathering shoe and wound onto a tubular sleeve located above the surface of the high speed winder. The tubular sleeve wrapped with strands can then be placed in a humidity and temperature controlled environment and conditioned for 8 hours. The size dry residue remains on the surface of the fiber. The amount of dry residue on the glass fiber strand will be from about 0.8 to about 1.3 wt% based on the weight of the strand. The resulting strand can be twisted and wound on a bobbin using a conventional threading machine. The strands thus produced can be evaluated for broken filaments using a broken filament detector of the type described in U.S. Pat. No. 4,610,707, and broken filaments for 1000 yards can be measured. . The test results are shown in Table 4.

In Table 3, no silylated RP polymer was used,
4 illustrates four reference formulations with separate or different silane coupling agents and cationic lubricants. Table 3 also shows some formulations using the silylated RP polymer in wt% solids of the ingredients.

[0099]

[Table 3]

Some of the sizing formulas shown in Table 3 are starch size yarns shown in the Examples of Table 4.
It was used to produce a sized yarn). Table 3
And the starches used in Table 4 are commercially available. Amize-213 corn starch manufactured by American Maze-Products, Inc. of Hammond, Indiana was used as the amize starch.

As the national starch, National 1554 potato starch manufactured by National Starch and Chemical Co. was used. As the Cato starch, Kato-75 cationic starch manufactured by National Starch and Chemical Co. was used.

[0102]

[Table 4]

Table 4 shows data on the effect of silylated RP polymer in glass fiber-yarns, which yarns have the exemplified fiber-sized G-75.
It has a structure of. Tensile strength is ASTM D5
Tested according to the method of 78-90, broken filaments for 1000 yards were tested by the broken filament detector described above. The ash content by weight% was obtained from the sizes used to make some specific size yarns shown in Table 4. The method was performed by drying the size components and thermodrying the dried residue using a PerkinElmer TGA instrument.

The sample was heated in air for decomposition.
The temperature starts from room temperature and is 20 ℃ until 650 ℃ is obtained.
I raised it at a rate of / minute. Table 4 shows that the size glass fiber with silylated RP polymer-yarn has better tensile strength compared to the commercial sample without silane coupling agent, and also the monomer silane coupling added to the sizing composition. It shows that the silane concentration as an agent is very close to that of the sample of Reference Example 2. Further, a formulation using a silylated RP polymer (13)
The average number of broken filaments of (20) to 2.92 was 2.92. The high silane content ash content of Reference Example 2 was for a commercial sample having an ash content of 0.33 wt% and a yarn containing a silylated RP polymer having an ash content of 0.57 wt%. It was 2.36% by weight.
Therefore, Table 4 shows that the yarns having the silylated RP polymer of the present invention have good tensile strength and low breaking filaments, while the amount of ash remaining on the yarn after heat cleaning is low.

Although the present invention has been described with reference to certain specific examples and embodiments, it is not limited to the examples and embodiments described above.

[0106]

According to the silylated polyamine polymer of the present invention, it is possible to give a size suitable for a textile strand. Other effects are as described above.

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Richard Paul Bieber United States, 15129 Pennsylvania, Library, Annette Abu Nu 1524 (72) Inventor Robert George Bryody United States, 15613 Pennsylvania, Apollo, Jackson Drive 622 (72) Invention Luis Jay Namesman Young Drive 301, Apollo, 15613 Pennsylvania, USA

Claims (27)

[Claims] 1. (I) (a) a polyamine having an acid moiety from a free amine and a polyfunctional fatty acid material, (b) a condensation product of a polyfunctional acid and a polyamine, and (c) a chain having a fatty acid moiety. extended polyamine, (d) acylated polyalkyleneamines, (e) a polyamine, condensation products of fatty acids and dimer acid, and (f) the formula H ₂ N-
_{(C n H 2n NH) x} -H ( wherein, n about 2-6 range,
x is in the range of 2 to 6), and a polyamine containing 3 or more amine groups having 3 or more amine groups and a polyamine polyamide prepared by condensing a monofunctional acid. A silylated polyamine polymer prepared by reacting a polyamine-containing polymer having one or more kinds of free amine groups, and (II) an amine-reactive organoalkoxysilane and a hydrolysis product thereof. 2. The polyamine of (I) has 1 to 1 carbon atoms.
The silylated polyamine according to claim 1, which is an acylated polyalkyleneamine prepared from a linear poly-2-oxazoline having a degree of polymerization of 8 to 22 having 17 alkyl substituents in the 2-position. 3. The polyamine of (I) is a chain-extended polyamine having a fatty acid moiety, and the polyamine has the general formula H ₂ N— (C _n H _2n NH) _x —H (where n is A silylated polyamine according to claim 1 which is a chain extended polyamine having a range of from about 2 to 6 and x ranging from 2 to 6 and containing 3 or more amine groups and containing a predominant amount of diamine. 4. A silylated polyamine according to claim 3, wherein the chain extender used to prepare the chain extended polyamine is a difunctional organic compound. 5. The chain-extended polyamine is diethylenetriamine (DETA), triethylenetriamine (TETA), tetraethylenepentamine (TEP).
A), pentaethylenehexamine (PEHA), dipropylenetriamine (DPTA), tripropylenetetramine (TPTA), tetrapropylenepentamine (TP
A polyalkyleneamine selected from the group consisting of PA), pentapropylenehexamine (PPHA), dihexamethylenetriamine (DHMTA) and a mixture thereof, which is present as a single compound, a plurality of compounds or a mixture of isomers. The silylated polyamines described. 6. The silylated polyamine according to claim 1, wherein the polyamine of (I) is the polyamine polyamide of (f). 7. The silylated polyamine according to claim 1, wherein the polyamine is a condensation product of a polyamine and a dimer acid which is a mixture of a fatty acid and a polyalkylene polyamine homolog. 8. A silylated polyamine according to claim 7, wherein the polyalkylene polyamine mixture is prepared by condensing ethylenediamine with acrylonitrile to form N-cyanoethyl-ethylenediamine which is reduced by catalytic hydrogenation. 9. The silylated polyamine according to claim 1, wherein the polyamine is a product obtained by condensing the polyamine with a polyfunctional acid. 10. The polyamine is a condensation product of a polyamine, a fatty acid and a dimer acid, and the dimer acid is 8 to 1
A method prepared from a fatty acid having 8 carbon atoms.
The silylated polyamines described. 11. The silylated polyamine according to claim 1, wherein the polyamine is a chain-extended polyamine having a fatty acid obtained by the following reaction. _{(I) NH 2 = (R} -NH) x -R-NH 2 + (II) (Q) p R'-R 1 -R' (Q) p (III) CH 3 - (CH 2) y -COOH To produce the following products (IV), (V) and (V
A mixture of I) (VI) (IV) and / or (V) having a repeating unit moiety containing one or more of the following branched chains (VII), (VIII) and (IX): (In the formula, p, w, x, y and z are integers, and p is 1
Or 0, x and y are values in the reactants, w and z are values giving a molecular weight up to about 50,000 Mw, R is a lower alkyl group, R'is a carbonyl group, an alkyl group, an oxirane group or a diisocyanate group; R ₁ Is 2 to 15
Bifunctional aryl radicals, bifunctional alkyl radicals and / or alkylene radicals having 4 carbon atoms; and Q is an OR or a halide and R ^'* is a urea functionality obtained by reacting an amine with an isocyanate. Or a cleaved oxirane group, Q is OR or a halide when R'is a carbonyl group, Q is a halide when R'is a lower alkyl group, p = 0 when R'is an oxirane group; and Polyamide I has a molecular weight. Is present in the reaction product in favor of structure V, structure VI is kept to a minimum, and unreacted secondary nitrogen groups are present in the reaction product due to the water solubility of the reaction product. The reaction is carried out as if 12. The (I) polyamine is NH ₂ — (CH _{2
-CH 2 -NH) 3 -CH 2 -CH} 2 -NH 2; (I
I) bifunctional organic compound _{C 2 H 5 O (O)} C-CH 2
_{-CH 2 -C (O) OC 2} H 5 and (III) a fatty acid material is _{CH 3 (CH 2) 6 COOH} , (II) and (III) primarily than mixture was added continuously the structure V 11. The reaction is carried out to form
The silylated polyamine polymer described. 13. The silylation according to claim 11, wherein the difunctional organic compound (II) is a compound whose bifunctional moiety is capable of reacting with the active hydrogen-containing nitrogen of the residual amine of the polyamine to form a covalent bond. Polyamine polymer. 14. A compound in which the difunctional organic compound (II) has a functional moiety selected from carboxylic acids, carboxylic acid esters, carboxylic acid anhydrides, epoxides or glycidyls; halides, isocyanates and suitable mixtures thereof. The silylated polyamine polymer according to claim 11, which is 15. The amine-reactive organofunctional silane of (II) has the formula: X _a —Si (OR) _b , where X is a moiety capable of reacting with active hydrogen present on the residual amine of the polyamine. An organic residue having, which is selected from the group consisting of an epoxy or glycidyl group, an isocyanate group, an ester group, a halogenated alkyl group and an acryloxy group, a is an integer of 1 to 2, and b is equivalent to 4-a. R is a hydrogen atom, an alkyl residue having 1 to 6 carbon atoms, an alkylaryl residue having 6 to 10 carbon atoms, an aryl residue or a cycloalkyl residue; or b is greater than 1. When it is a mixture of a hydrogen atom and one of said organic residues].
The silylated polyamine polymer described. 16. The amine-reactive organofunctional silane is selected from the group consisting of (a) epoxy organofunctional silane ester, (b) isocyanate organofunctional silane ester, and (c) acryloxy-containing organofunctional silane ester. The silylated polyamine according to claim 15. 17. An epoxy organofunctional silane ester (a) wherein the alkoxy group can be methoxy or ethoxy, gamma-glycidoxyalkyltrialkoxysilane, deltaglycidoxybutyltrimethoxysilane and beta-glycidoxyethyl. Selected from the group consisting of triethoxysilane; the isocyanate organofunctional silane (b) is gamma-isocyanatopropyltriethoxysilane, and the acryloxy-containing organofunctional silane ester (c) is gamma-methacryloxypropyltrimethoxysilane, gamma. -Acryloyloxypropyltrimethoxysilane, gamma-methacryloxypropyltriethoxysilane and gamma-methacryloxypropyltris- (2-ethoxyethoxy) silane. 6. The silylated polyamine according to 6. 18. The silylated polyamine of claim 1, wherein the molar ratio of polyamine-containing polymer to amine-reactive silane is in the range of about 1: 0.5 to about 1: 3. 19. The reaction is a lower alkyl alcohol; polyalkylene glycol, alkyl ethers thereof,
The silylated polyamine according to claim 1, which is carried out in the presence of a solvent selected from the group consisting of ethoxylated alcohol and water. 20. A silylated polyamine according to claim 1, wherein a predominant amount of unsilylated reaction product is present after completion of the reaction. 21. A chemical treatment composition for treating a substrate, which comprises the silylated polyamine according to claim 1 and a predominant amount of water. 22. Film-forming polymers, nonionic lubricants, cationic lubricants, antistatic compounds, organofunctional coupling agents, waxes, emulsifiers, surfactants, thixotropic agents, defoamers, and these. The chemical treatment composition according to claim 21, further comprising at least one component selected from the group consisting of a mixture of any two or more thereof. 23. The chemical treatment composition is a poly (vinylpyrrolidone) homopolymer, a polyvinylpyrrolidone copolymer,
23. The chemical treatment composition of claim 22, containing a film-forming polymer selected from the group consisting of polyvinyl acetate homopolymers and polyvinyl acetate copolymers. 24. A substrate selected from the group consisting of polymer fibers, glass fibers, glass substrates and metal oxide substrates on which the silylated polyamine polymer of claim 1 is attached. Material. 25. A silylated polyamine polymer according to claim 1, and (a) at least 35% by weight of at least one starch of the non-aqueous component of the composition present as a predominant amount of film former, (b) water. Selected from the group consisting of added vegetable oils, fatty acid esters of non-polymeric polyhydric alcohols, mineral oils and mixtures thereof, wherein the oil is present at 25-40% by weight of the non-aqueous components of the composition and the ratio of oil to starch is 0. A nonionic lubricant in the range greater than 4 and up to 1.5; (c) at least one oil emulsifier present in an amount effective to form an oil-in-water emulsion; The amount of oil that provides integrity and is present in the range of 1 to about 20% by weight of the non-aqueous components of the composition, and from greater than 5% by weight to 40% by weight. It decreases concomitantly, made of the second film forming agents other than starch, about a total amount of the aqueous composition non-aqueous component 1
To about 30% by weight, and the size residue on the glass fiber due to loss on ignition is in the range of about 0.1 to about 5% by weight. 26. A fiber treatment with a cationic fiber lubricant comprising (a) applying the chemical treatment composition of claim 21 to fibers and (b) collecting the fibers into at least one bundle. Law. 27. The silylated polyamine of claim 1, wherein the reaction of one or more of the polyamine-containing polymer with the amine-reactive organoalkoxysilane is carried out at a temperature in the range of room temperature to 70 ° C. for about 15 minutes to about 8 hours. polymer.