JPS62225549A - Glass fiber sizing agent composition - Google Patents

Abstract

PURPOSE:The titled composition which has improved bundling properties of glass fibers and providing a thermoplastic resin composition having improved physical properties, obtained by blending a copolymer consisting of polymerization units of and alpha,beta-unsaturated dicarboxylic acid and an alpha,beta-unsaturated monocarboxylic acid with a silane coupling agent. CONSTITUTION:(A) 100pts.wt. copolymer which consists of A1: a polymerization unit of an alpha,beta-unsaturated dicarboxylic acid (e.g. fumaric acid, etc.) and A2: a polymerization unit of an alpha,beta-unsaturated monocarboxylic acid (e.g. acrylic acid, etc.) and has a molar ratio of polymerization of 10:90-90:10, preferably 20:80-80:20 is optionally dissolved in an aqueous medium under an alkali condition and blended with (B) 0.5-1.5pts.wt. silane coupling agent (e.g. gamma- aminopropyltriethoxysilane, etc.) to give a sizing agent composition. The composition preferably contains 2-10wt% component A and 1-20wt% component B.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a glass fiber sizing agent for reinforcing thermoplastic resins. More specifically, the present invention relates to a glass fiber sizing agent composition that provides a reinforced thermoplastic resin composition with excellent glass fiber cohesiveness and excellent physical properties.

[Conventional technology]

Conventionally, sizing agents for glass fibers containing a heavy substance having a calgexi group have been proposed as follows.

Japanese Patent Publication No. 51-2550 discloses that an alkyl acrylate in which the alkyl group has 1 to 12 carbon atoms, 25% by weight or more, α
A glass fiber size composition for reinforcing olefinic resins is disclosed which contains a copolymer of 1 weight or more of β-monoethylenically unsaturated cargenic acid and a vinyl monomer other than the above-mentioned monomers. The publication specifically discloses, for example, acrylic acid, methacrylic acid, itaconic acid, fumaric acid, and 20-ton acid as the α,β-monoethylenically unsaturated carboxylic acid.

JP-A-49-11A993 describes alkyl acrylates in which the alkyl group has 1 to 12 carbon atoms, 10% by weight or more, α,β-monoethylenically unsaturated carboxylic acids, 1% by weight or more, α,βl - A thermoplastic resin containing a copolymer produced from a blend of 1 i% or more of monoethylenically unsaturated hydrohydride ester and the balance weight% of vinyl monomers other than the above monomers (excluding vinyl acetate). A reinforcing glass fiber size is disclosed. In the same publication, acrylic acid, methacrylic acid, itaconic acid, fumaric acid, and 20 tons are specifically described as α,β-ethylenically unsaturated carboxylic acids, and these are preferably 1 to 8% by weight. It is also disclosed that the vehicle is owned.

JP-A-52-11 (L996) discloses nonionic polyethyl acrylate with a molecular weight of 100,000 or more, N-methylolacrylamide/vinegar rice vinyl random copolymer, and cationic dimethylaminozorobylamine and benzurgon. JP-A-6A-A4,555, which discloses glass fibers having a blend of acid condensates adhered to the surface, discloses a copolymer of maleic anhydride and an unsaturated monomer and a silane-based A glass fiber-reinforced thermoplastic resin is disclosed in which the thermoplastic resin is reinforced with glass fibers surface-treated with a coupling agent.The publication discloses that the above-mentioned unsaturated monomers include methylene, α-methylstyrene, , butadiene, isoprene, chloroprene, 2,5-dichlorobutadiene,
Only 1,5-intadiene, cyclooctadiene/, methyl acrylate, ethyl acrylate, methyl methacrylate and ethyl methacrylate are specifically mentioned.

JP-A-60-44951 discloses maleic anhydride and an ethylene hydrocarbon having 2 to 5 carbon atoms (or vinyl acetate).
A glass fiber for reinforcing plastics surface-treated with a copolymer with a silane coupling agent and a silane coupling agent is disclosed. The copolymer does not include acrylic acid or methacrylic acid as described above.

JP-A-60-15845 discloses a polyamide selected from nylon 66, nylon 6, nylon 610, and copolymers thereof, 10 to 60% by weight of a reinforcing filler, and a polymer reactive with the terminal groups of the polyamide. A polyamide product for contact with antifreeze compositions under high agitation conditions is disclosed having a functionalized copolymer on the order of 0.1 to 10 wt s. The same publication states that the above copolymer is
Residues from ethylenically unsaturated materials having functional groups should be contained in an amount of 50 mole or less. copolymers of CalM/acid-containing monomers (or carboxylic anhydride-containing monomers) and olefins, copolymers of copolymerizable carboxylic acid monomers (or copolymerizable carboxylic anhydride monomers) and styrene A copolymer is disclosed;
As a specific example, a copolymer consisting of 72 parts by weight of methyl methacrylate, 3 parts by weight of ethyl acrylate, and 25 parts by weight of methacrylic acid is described as a polymer with the largest allocation of methacrylic acid. However, in the above publication, polyamide,
It only discloses blends of Japanese horse mackerel and Japanese mackerel, and does not disclose the use of 17IC aminosilane.

[Problems to be solved by invention]

Therefore, an object of the present invention is to provide a glass fiber wasting agent composition for reinforcing a thermoplastic resin having a novel composition.

Another object of the present invention is to provide a glass fiber sizing composition which provides a thermoplastic resin composition having excellent glass fiber bundle properties and excellent physical properties such as Izot impact strength and water resistance strength.

Further objects and advantages of the present invention will become apparent from the description below.

[Means and effects for solving the problems] According to the present invention, the objects and advantages of the present invention are as follows: (A) α, β-unsaturated dicargenic acid polymerized units and α, β
-, β-monocarboxylic acid polymer units, and the polymerization molar ratio of α, β-unsaturated unsaturated decal polymer units to α, β-unsaturated heptanocarboxylic acid polymer units is 10:9Q.
This is achieved by a glass fiber sizing composition for thermoplastic resin reinforcement comprising a copolymer in the range of 90:10 and (B) a silano coupling agent.

One component (A) constituting the sizing agent composition of the present invention
As mentioned above, the copolymer which is the component) consists of polymerized units of α,β-unsaturated dicargonic acid and polymerized units of α,β-unsaturated monocargenic acid.

α,β-unsaturated unsaturated dinorbic acids are particularly preferably dicarboxylic acids having 4 or 5 carbon atoms, such as maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, especially maleic acid, fumaric acid and itaconic acid. used.

As α, β-, β-monocarboxylic acids, monocarboxylic acids having 5 or 4 carbon atoms, such as acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, and isocrotonic acid, particularly acrylic acid or methacrylic acid are particularly preferred. used.

Two or more types of α, β-, β-dicarboxylic acid and α, β-, β-monocarzanoic acid can be used in combination.

The above copolymer of component (A) is composed of polymerized units of α,β-unsaturated dinor and polymerized units of α,β-unsaturated monocargenic acid in a molar ratio of the former polymerized units to the latter polymerized units. is 10:90 to 90:10, preferably 20:80 to
Contained in a ratio of 80:20.

Further, the above polymer preferably ranges from about 50 to 100゛0
, particularly preferably a degree of polymerization of 100 to 2,000.

The copolymer of component (g) of the present invention is generally soluble in water, and is easily prepared in the form of an aqueous solution suitable for treating glass fibers. When preparing an aqueous solution, the copolymer can also be neutralized with an alkaline compound. Neutralization can increase the viscosity of an aqueous solution.

To make it alkaline, alkali metal compounds, ammonia, amines, etc. are preferably used.

The above-mentioned round component preferably occupies 2 to 10% by weight in the sizing composition of the present invention.

The other component (B) constituting the sizing agent composition of the present invention
component) is a cyrano coupling agent.

Compounds suitable as silane coupling agents include, for example, r
-aminopropyltriethoxysilane, N-β-(aminoethyl)-r-aminepropyltrimethoxysilane,
N-β-(amineethyl)-N/-β'-(aminoethyl)-γ-aminozolopyltrimethoxysilane, γ-ureidozolobyltriethoxysilane, γ-chlorozolobyltrimethoxysilane, vinyltrichlorocidine, Vinyltriethoxysilane, vinyl-trisC7/-'toxyethoxy)silane, γ-methacryloxypropyltrimethoxysilane, β-(5,4-epoxycyclohexyl)ethyltrimethoxysilane, r-glycidoxynolopyltrimethoxysilane Alternatively, it may be γ-merkanotoguccobyltrimethoxysilane or the like.

In the sizing agent composition of the present invention, the silane coupling agent preferably accounts for 1 to 20% by weight.

The above (g) component) means that the ratio of the above CB) component is preferably [L5 to 1
．． 5 parts by weight, particularly preferably 5 to 1.0 parts by weight per liter.

The sizing agent composition of the present invention can be produced by dissolving the polymer of component (A) in an aqueous medium, if necessary under alkaline conditions, and mixing it in that state with a silano coupling agent.

The sizing agent composition of the present invention can further contain a lubricant. As the lubricant, for example, mineral oil-based, paraffin-based, fatty acid amide-based, metal soap-based, silicone-based, and polyethylene glycol-based surfactants are preferably used. The lubricant is used in an amount ranging from about 15 to 5.0 parts by weight per 100 parts by weight of component (A).

The sizing composition of the invention preferably has a loss on ignition of 5 to 150% by weight, more preferably 10% by weight as a solid.
It is applied to the glass fibers in an amount ranging from 100 to 100 weights.

Glass fibers sized with the sizing composition of the present invention can be made of, for example, polyamides (poly ε-caprolactam, polyhexamethylene azinogamide, etc.), saturated tetraesters (polyethylene terephthalate, polytetramethylene terephthalate, etc.), polyolefins (polypropylene, modified polypropylene, etc.), polyphenylene oxide 9, polyoxymethylene, acrylonitrile-styrene copolymer, acrylonitrile-styrene-butadiene, en-rubber, chloropre/rubber, nitrile rubber, etc.; or thermosetting of unsaturated polyester resin, phenol resin, etc. Glass fibers sized with the sizing agent composition of the present invention are particularly advantageously used for reinforcing polyamide resins.

The present invention will now be described in detail with reference to Examples, but the present invention is not limited in any way by these Examples.

In addition, the convergence of the glass fibers described in the examples was measured as follows.

The chopped strand 50f was placed in a 500cc graduated cylinder, vibrated for 2 minutes, and then the height of the chopped strand was measured to determine the degree of convergence. Put 50f (Pudstran) in a 5oocc beaker and add 1500r
After stirring for 2 minutes at a speed of 100 pm, the height of the chopped strands was measured, and another parameter (Kento resistance) was used to judge the degree of convergence.The quality of convergence was determined by these two
A comprehensive evaluation was made taking into account two parameters. The valley marks indicate the following levels.

Bulk height (澗) Focusing resistance (wx) ◎ mark 40 or less 40 or less O mark 40
~45 40~50Δ mark 45~50 5
0~60X mark 50 or more 60 or more
The tensile strength was determined by the method described in ASTM-D658, and the impact strength was determined by the method described in ASTM-D256 (Unichi).

The tensile strength when wet was measured after immersing a test piece for strength measurement in an antifreeze solution at 150° C. for 100 hours.

〔Example〕

Example 1 77-kfil 50 mole titacrylic rt1.70
The copolymer obtained from the malt mixture was dissolved in deionized water and then brought to a concentration of 28%! The pH was adjusted to 7-9 by adding 1% aqueous ammonia. Furthermore, the obtained aqueous solution is
A hydrolyzed solution of -aminopropyltriethoxysila/ was added and mixed to obtain a sizing composition having the following composition.

50 parts by weight of the above copolymer 28% ammonia water α5' deionized water
95.0' The above Cyjinda liquid was coated onto melt-spun glass filaments (diameter 13 μm) using an applicator to collect the glass filaments, and then wound into a single roll on a rotating drum.The fiber content was 5.
It was blended with nylon 6.6 to a concentration of 0% by weight and melt-mixed in an extruder to produce a glass fiber-containing pellet.

Test pieces were made from this glass fiber-containing pellet by injection molding, and various tests were conducted. The results are shown in Table 1 below.

Example 2 The same operation as in Example 1 was carried out except that a copolymer of itaconic acid (50 molti) and methacrylic acid (70 molti) was used instead of the copolymer of fumaric acid and acrylic acid. Various physical properties of the 6°6-nylon composition (glass fiber content 50% by weight) reinforced with glass fibers sized with the obtained sizing composition are shown in the first article.

Example 3 Completely the same as Example 2 except that a copolymer of maleic acid (50 mol) and methacrylic acid (70 mol %) was used instead of the copolymer of itacone and methacrylic acid. operated. The results are shown in Table 1.

Comparative Example 1 A polyurethane emulsion type sizing composition consisting of polyester polyol and tolylene diisocyanate was used as the sizing composition, and the other conditions were as in Example 1.
operated in the same way. The results are shown in Table 1.

Comparative Example 2 A solution prepared by dissolving 40 parts by weight of polyacrylic acid with a degree of polymerization of about IQ, 000 and 2 parts by weight of fumaric acid in 95 parts by weight of water was used as a sizing agent, and the other operations were the same as in Example 1. The results are shown in Table 1.

Example 4 As a sizing agent, the following composition: ammonia water with a concentration of 28% 15" deionized water
Using a 95.0” sizing composition,
The other operations were the same as in Example 1. The results are shown in Table 1.

〔Effect of the invention〕

As described above, the glass fiber sizing composition of the present invention is superior to glass fibers! ! E and provides a thermoplastic resin composition having excellent physical properties such as Izot impact strength and water resistance. In particular, the glass fibers treated with the sizing composition impart high initial strength and antifreeze penetration resistance to the reinforced resin composition when incorporated into the polyamide resin.

Claims (1)

[Scope of Claims] 1. (A) Consisting of polymerized units of α,β-monounsaturated dicarboxylic acid and polymerized units of α,β-unsaturated monocarboxylic acid, and polymerized α,β-unsaturated dicarboxylic acid; A thermoplastic resin comprising a copolymer in which the polymerization molar ratio of polymerized units to α,β-unsaturated monocarboxylic acid units is in the range of 10:90 to 90:10, and (B) a silane coupling agent. Glass fiber sizing agent composition for reinforcement.