JPS62292658A - Water-based sizing agent for glass fiber - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] 3. Detailed Description of the Invention (Field of Industrial Application) The present invention relates to an aqueous sizing agent for glass fibers, and in detail:
This invention relates to an aqueous sizing agent for glass fibers which can provide a glass fiber-reinforced thermoplastic resin which has strong cohesiveness, does not yellow even at high molding temperatures of 200° C. or higher, has a good appearance, and has excellent mechanical properties.

<Conventional technology> Glass fibers are used as reinforcing materials for various synthetic resins, but in recent years glass fiber reinforced thermoplastic resins (F'RTP) have been used as reinforcing materials.
has been attracting attention due to its good moldability and secondary processability.

By the way, glass fibers are made by spinning molten glass to form filaments, then bundling several hundred filaments into one strand, which is then cut into lengths of 3 to 6 as+ to make chopped strands. Or, it can be obtained by gathering dozens of them to form a roving, but it is used to protect the filament by preventing yarn breakage and fuzzing caused by friction during manufacturing of glass fiber or blending with thermoplastic resin. Sizing agents are used in Therefore, the binder, which is the main component of the sizing agent, uses glass fJ! Strong cohesiveness is required to bond and protect the fiber strands.

Polyvinyl acetate is well known as such a binder, but this resin has poor heat resistance, so the molding temperature is 2.
For example, when applied to d-lyamide resins (6-nylon, 6.6-nylon, etc.) at temperatures as high as 00°C or higher, they tend to be colored due to decomposition and have low affinity with the matrix polyamide resin. The drawback was that the high-power φ machining of the molded product was low.

Therefore, in recent years, the use of polyurethane aqueous dispersions as an effective binder when a polyamide resin is used as a matrix has been studied. Polyurethane water dispersion has high cohesiveness as a binder due to its excellent mechanical properties.
In addition, since it has a good compositional affinity for various molding thermoplastic resins including the aforementioned polyamide resin, glass fiber-reinforced thermoplastic resins using this resin are characterized by high strength.

<Problems to be Solved by the Invention> However, conventional aqueous polyurethane dispersions using aromatic isocyanates turn yellow during high-temperature molding such as extrusion molding or injection molding (molding temperature is 200°C or higher), and molded products The problem of unfavorable appearance still remained.

In order to solve this problem, attempts have been made to use aliphatic or alicyclic isocyanates instead of aromatic isocyanates, but although some improvement in yellowing has been observed, the results are still sufficiently satisfactory, especially for light-colored molded products. At present, it is not possible to obtain a suitable external color tone.

Means to solve problems〉 The present inventors relate to an aqueous sizing agent for glass fibers.

Especially when reinforcing various thermoplastic resins with high molding temperatures of 200°C or higher, this glass has excellent glass fiber cohesiveness, does not yellow during high-temperature molding, and provides FRTP with excellent external color tone and mechanical properties. As a result of intensive research on aqueous sizing agents for textiles, we found that the isocyanate component of alicyclic and/or aliphatic isocyanates and at least one selected from hydrazines, dihydrazides, and semicarbanides.
The present inventors have discovered that the above-mentioned performance can be demonstrated by using an aqueous polyurethane dispersion obtained by combining a compound of .tji with a chain extender as a .9 inder, and have completed the present invention.

That is, the present invention provides chain elongation of (A) a polyol component, (B) an isocyanate component of an alicyclic and/or aliphatic isocyanate, and (Q) a compound of at least lfi selected from hydrazines, dihydrazides, and semicarbanides. The purpose of the present invention is to provide an aqueous sizing agent for glass fJ1.m containing an aqueous urethane dispersion obtained from a urethane agent as a binder.

For the polyol component used in the production of the polyurethane aqueous dispersion (~), all raw materials used in the synthesis of ordinary polyurethane can be used, for example, molecules -[200~
10,000, preferably 3oO to 5000 polyester, ? Liether, polycarbonate, polyester amide, polyacetal.

Examples include polythioether and polybutadiene glycol.

Typical polyesters and polyethers as polyol components will be described in detail below. Polyesters include ethylene glycol, gummy pyrene glycol,
．． 3-7'-entanediol, 1,4-butanediol, 1.5-e-entanediol, 1.6-hexanediol, neo-e/tyl glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol ( MW300-6000)
, diethylene glycol, triflopyrene gellicol,
1,4-cyclohexanediol, 1,4-cyclohexane dimetatool, bisphenol A, hydroquinone and their alkylene oxide adducts, glycerin,
A diol or polyol component such as trimethylolethane, trimethylolethane, pentaerythritol, sorbitol, etc. and succinic acid.

Adipic acid, azelaic acid, sepa-hexanoic acid, doricandicarzanic acid, maleic anhydride, hexamaric acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarmenic acid, terephthalic acid, isophthalic acid, Phthalic acid, 1.
4-naphthalene dicarboxylic acid, 2.5-s7tale dicarboxylic acid, 2.6-nanotale dicarmenic acid, naphthalic acid, piphenylsocarmenic acid, 1,2-bis(phenogyshi)ethane-pIP'-dicarboxylic acid , trimellitic acid, pyromellitic acid, and anhydrides or ester-forming derivatives of these dicarboxylic acids or polycargenic acids; p
- In addition to polyesters obtained by dehydration condensation reaction with acid components such as hydroxybenzoic acid, p-(2-hydroxyethoxy)benzoic acid, and ester-forming derivatives of these hydroxyl phosphoric acids, cyclic polyesters such as C-caprolactone Examples thereof include polyesters obtained by ring-opening polymerization reaction of ester compounds and copolyesters thereof.

Examples of polyether include ethylene glycol, diethylene glycol, triethylene glycol, 1!2-propylene glycol, trimethylene glycol, ll3-
Butylene glycol, tetramethylene glycol, hexamethylene glycol, decamethylene glycol, glycerin, sorbitol, aconitic acid, trimellitic acid, hemimellitic acid, phosphoric acid, ethylenenoamine, glopylenenoamine, diethylenetriamine, triisoglono9olamine , pyrogallol, dihydrobenzoic acid, hydroxyphthalic acid, 1*213-gulonocuntrithiol, etc., using as an initiator one or more compounds having at least two active hydrogen atoms, such as ethylene oxide, propylene oxide, butylene. Oxide, styrene medium side.

Examples include monomers such as epichlorohydrin, tetrahydrofuran, cyclohexylene, etc., obtained by cycloaddition polymerization of 1 m or more of monomers by a conventional method.

Isocyanate component CB) is essentially a cycloaliphatic and/or aliphatic isocyanate.

For example, tetramethylene diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene! Diisocyanate, lysine diisocyanate, inphoronoisocyanate, 1,3-cyclobenzeni diisocyanate, 1,3-cyclohexylene diisocyanate,
l, 4-cyclohexylene diisocyanate, 1,3-
No(isocyanatomethyl)cyclohexane, l, 4-
(isocyanatomethyl)cyclohexane, 4.4'
-non-chlorohexylmethane diisocyanate and trimer compounds thereof. In order to increase the strength of the molded product, it is particularly preferable to use alicyclic isocyanate.

Also, a chain extender (q is 1, such as hydranone).

Hydrazines such as NJ-trimethylhydrazine and 1,6-hexamethylenebishydrazine; Sohydrazides such as adipic acid zohydrazide, glutaric acid nohydrazode, sebacin-branched zohydrazode, and isophthalic acid zohydrazode; β-
Semi-carbanodonoropionic acid hydrazide, 3-semicarbanodo-zolopyl-carbazate, semi-carbazido-3-semi-carbazidomethyl-3,5,5-
It is essential to use at least one compound selected from semicarbacites such as trimethylcyclohexane. It is desirable to use hydranones, zohydranodes, and preferably hydrazones because they are inexpensive, easy to handle, and have good physical properties. In addition to chain extender (q), in some cases other chain extenders (
11 can be used. Such chain extenders include glycols or polyols, such as evaporated ethylene glycol, diethylene glycol, propylene glycol,
l, 4-butanediol, hexamethylene glycol,
Examples include neopentyl glycol, chrycerin, trimethylolethane, trimethylolethane, pentaerythritol, sorbitol, etc. Polyurethane aqueous dispersions can also be produced by any conventionally known method, for example: Polymers or polymers blocked with t-blocking agents (active water-based compounds such as oximes, alcohols, phenols, mercaptans, C-caprolactone, bisulfite, etc.) are forced using emulsifiers and mechanical shearing force. method of dispersing in water.

■ A method in which a urethane prepolymer with terminal isocyanate groups is forcibly dispersed in water using an emulsifier and mechanical shearing force, and then reacted with a chain extender in water to increase the molecular weight.

(2) A method in which hydrophilicity is imparted by attaching an ionic group such as a sulfonic acid group, amine group, or carmexyl group to the 'JjJId or end of a polyurethane polymer, and the polymer is dispersed or dissolved in water by self-emulsification.

(2) A method in which a water-soluble polyol such as polyethylene glycol or monoalkoxy polyethylene glycol is used as the main raw material polyol for polyurethane, and the polyurethane resin is dispersed or dissolved in water.

etc., and methods that combine these methods.

The obtained polyurethane aqueous dispersion is further treated with a coupling agent,
It is used as a water-based sizing agent by adding lubricants and other auxiliary agents. Therefore, from the viewpoint of compatibility with these additives, the aqueous polyurethane dispersion should be a polyurethane aqueous dispersion that is substantially nonionic in the system and can be obtained by the method ①, ② or ②. preferable. Particularly preferred is the manufacturing method (2) which allows the molecular weight of polyurethane to be increased. Specifically, the above-mentioned (A) polyol component, (B) isocyanate component of alicyclic and/or aliphatic isocyanate, and optionally ρ) other chain extenders are used in an amount in which the isocyanate is in excess relative to the active hydrogen. A molecular weight of 500 to 10,000, preferably 800 to 50, having a terminal isocyanate group reacted in a proportion such that
After making it into a prepolymer of o.

This prepolymer is forcibly emulsified and dispersed together with an emulsifier aqueous solution using mechanical shearing force, and further (qhydrazines,
A chain extension reaction is carried out in water using a chain extension agent of at least one compound selected from dihydrazides and semicarbanides, and the molecular weight is 5000 or more, preferably 100.
This is a method of preparing an aqueous dispersion of high molecular weight urethane having a molecular weight of 00 to 1,000,000.

The prepolymerization reaction in the above method can be carried out without a solvent or in the presence of a solvent, and such solvents include, for example, ketones such as acetone, methyl ethyl ketone, and cyclohexano.

Ethers such as tetrahydrofuran and nooxane, noesters such as ethyl acetate, n-hebutane, n-hexane,
Examples include hydrocarbonized water wings such as cyclohexane, benzene, toluene, and xylene, and chlorinated carbonized leaves such as trichloroethane and nochloromethane.

Furthermore, as the emulsifier used for emulsifying and dispersing the above-mentioned GLE/IJmer, commercially available emulsifiers, especially nonionic emulsifiers, can be used, such as polyoxyethylene argyl ether, polyoxyethylene allyl ether, polyoxyethylene polyoxy Examples include propylene glycol.

The aqueous sizing agent of the present invention contains a coupling agent, a lubricant, and other auxiliary agents in addition to the polyurethane aqueous dispersion, and is put to practical use.

Coupling agents are conventionally known ones, such as γ
-glycidoxyglobiltrimethoxysilane, γ-chloropropyltrimethoxysilane, r-mercaptoglobiltrimethoxysilane, γ-aminoglopyltrimethoxysilane, r-amino 760 pyltriethoxysilane, N-β-amino Ethyl-γ-aminonoropyltrimethoxysilane.

N-β-aminoethyl-γ-aminopropyltriethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane, bis-β-hydroxyethyl-γ-aminopropyltriethoxysilane, r-ureidopropyltriethoxy Examples include organic silane compounds such as silane.

Among them, γ-aminoglopyltriethoxysilane, N
An organosilane coupling agent having an amine functional group such as -β-aminoethyl-γ-aminoglopyltriethoxysilane is preferred.

Examples of the lubricant include conventional cationic lubricants such as a condensate of a polyamine such as triethylenetetramine pelargonate and a straight chain fatty acid.

To prepare the aqueous sizing agent of the present invention, the solid content of the polyurethane water component/coupling agent/lubricant is generally 1 to 2010.1 to 57 o, HN3, respectively.
(wt%), preferably 3-1010.2-210.0
It is blended at a ratio of 5 to 1 (heavy) and put into practical use.

If necessary, the aqueous sizing agent may also contain auxiliary agents such as antistatic agents such as alkyl or allyl sulfonates or sulfates of triethanolamine.

The aqueous sizing agent for glass fibers of the present invention may contain conventionally known polyvinyl acetate copolymer Emulno 1, epoxy resin Emulno 1, within a range that does not impair the effects of the present invention.
A binder such as a polyester aqueous dispersion can also be used in combination.

The aqueous sizing agent for glass fibers of the present invention comprising the above-mentioned components is applied to glass fibers according to a conventional method. For example, it can be applied by a size applicator when spinning molten glass from a bushing to create glass fiber filaments.

The amount of sizing agent deposited on the glass and fibers is 0.2 to 2.0% relative to the glass fibers in terms of solid content. It is preferable that it is O-heavy and Jt-chi.

Effects> The aqueous sizing agent for glass and steel obtained by the present invention exhibits excellent convergence properties for glass fiber strands, and can be used to bind thermoplastic resins without causing yarn breakage or fuzzing in chopped strands. In addition, when this glass JXm is applied to thermoplastic resins that require a molding temperature of 200°C or higher, there is no yellowing due to decomposition or deterioration of the binder during high-temperature molding, and there is no yellowing of the matrix. Because it has extremely excellent affinity and compatibility with thermoplastic resins, it has become possible to provide glass fiber reinforced thermoplastic resin (FRTP) molded products with extremely good external color tone and strength properties.

<Examples> The present invention will be further explained below with reference to Examples, but the present invention is not limited thereto. However, all parts and parts in the examples are based on weight.

Example 1 Polyzolopylene glycol 5F4 with an average molecular weight of 1000
and 26 parts of ethylene glycol while stirring.
-Non-chlorohexylmethanezoisoneane-) 416 parts t
'' and reacted at 70°C for 3 hours to obtain a prepolymer with an isocyanate content of 4.9%.Next, 40 parts of toluene was added to the above prepolymer 1004, and the resulting brepolymer solution was Added 75 parts of an aqueous solution containing 6 parts of polyoxyethylene/polyoxypropylene glycol having a molecular weight of about 16,000 (polyoxyethylene content: about 80%, molecular weight of polyoxypropylene: 3,250).

Stir vigorously with a stirrer to obtain an emulsified dispersion of prepolymer, and add 55 parts of an aqueous solution containing 2.98 g of 100 hydrated hydrazone with stirring to perform a chain extension reaction to obtain a polyurethane aqueous dispersion with a solid content of 40%. body-CI) was obtained.

Using this aqueous dispersion (I)', an aqueous sizing agent having the following composition was prepared.

Polyurethane water dispersion - (■) (solid content 40%)
10 parts r-aminopropyltriethoxysilane
0.81 Silazole 85A (ICI lubricant) 0.11 Water
89. l# Attach the above aqueous sizing agent to the glass fiber filament i 0
．． 5% and dried at 130° C. for 10 hours to create chopped strands of 6jElK. The resulting chopped strands have a glass fiber content of 30
% with 6-nylon resin pellets for general molding, mixed with an extruder, extruded, and cut to obtain glass fiber-containing pellets.

A test piece was made from these 4 pieces using an injection molding machine, and its color tone was measured using a color machine (Nippon Denshoku Kogyo (Inu)). Judgment was made based on the color difference with non-glass fiber reinforced 6-nylon resin, and further ASTM-D Tensile and impact tests were conducted based on -638 and D-256.

Example 2 Average molecular weight [2000 butylene adi-4-doriester 476 parts, 1,4-butanediol 24 parts, inphorone diisocyanate 222 parts, 100% water-containing hydrazine 2
Polyurethane aqueous dispersion (It) with a solid content of 40% was obtained from 4.8 parts in the same manner as in Example 1, and thereafter test pieces of glass fiber reinforced 6-nylon resin were prepared in the same manner as in Example 1. , color, tensile and impact strength were evaluated.

Comparative Example 1 Glass 1 fiber reinforced 6 was produced in the same manner as in Example 1 using polyurethane aqueous dispersion (1) obtained by carrying out the same reaction except that ethylene diamine was used instead of hydranone in Example 1. - Two test pieces of nylon resin were prepared, and the color tone and strength were evaluated.

Comparative Example 2 In the same manner as in Example 1 using a polyurethane aqueous dispersion obtained by the same reaction except that tolylene diisocyanate was used instead of 4,4-dicyclohexylmethane diisocyanate in Example 1. Glass fiber reinforced 6
- Nylon resin test pieces were prepared and evaluated for color tone and strength.

Example 3 Polycaprolactone polyol 7 with an average molecular weight of 12,000
50 parts, 11.2 parts of Trimethylol Pro 14F.

4.4'-dicyclohexylmethane diisocyanate 2
A polyurethane aqueous dispersion with a solid content of 40 parts was prepared in the same manner as in Example 1 from 08 parts, 100 parts and 15.0 parts of hydrated hydrazine.
(V) was obtained, and thereafter, test pieces of glass fiber-reinforced 6-nylon resin were prepared in the same manner as in Example 1, and color tone, tensile strength, and bacterial strength were evaluated.

Example 4 Produced in the same manner as in Example 1 from 500 parts of glycerin-based polypropylene triol with an average molecular weight of 3,000, 500 parts of polypropylene glycol with an average molecular weight of 2,000, 200 parts of inholone isocyanate, and 20.0 parts of 100% water and drazine. A polyurethane aqueous dispersion (■) with a solid content of 40% was obtained. Thereafter, test pieces of glass fiber-reinforced 6-nylon resin were prepared in the same manner as in Example 1, and color tone, tensile strength, and impact strength were all evaluated. All milled rice is summarized in Table 1.

Claims (1)

[Claims] 1, (A) polyol component, (B) isocyanate component of alicyclic and/or aliphatic isocyanate, and (C
) An aqueous sizing agent for glass fibers containing as a binder an aqueous polyurethane dispersion obtained from a chain extender of at least one compound selected from hydrazines, dihydrazides, and semicarbazides.