JP2001354452A - Finishing agent for glass fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a finishing agent for a glass fiber which ensures superior adhesiveness, smoothness and flexibility for the glass fiber. SOLUTION: This finishing agent for a glass fiber comprises a polyvinyl alcohol resin (A) and polyalkylene glycols (B).

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a glass fiber treating agent, and more particularly, to a glass fiber treating agent comprising a polyvinyl alcohol resin having excellent adhesion, smoothness and flexibility to glass fibers. .

TECHNICAL FIELD OF THE INVENTION

[0002]

2. Description of the Related Art Usually, glass fibers are treated with a sizing agent immediately after spinning, and the use of such an agent protects the glass fibers from the effects of bending, abrasion, and the like on the glass fibers in the subsequent steps, Its main purpose is to prevent yarn breakage and fluffing.

[0003] Therefore, as such a treating agent, there is provided a treating agent which forms a protective coating on the surface of the fibers and bonds and bonds the fibers together to protect the fibers from thread breakage and fuzzing due to friction or the like. Is usually used. Conventionally,
Examples of such treating agents include aqueous dispersions of homopolymers or copolymers of olefinically unsaturated monomers such as vinyl acetate, acrylate, and styrene-butadiene, starch, and general polyvinyl alcohol resins. And the like are used.

[0004] However, the sizing properties of glass fibers treated with an aqueous dispersion or a water-soluble polymer solution of these synthetic resins are not always sufficiently satisfactory. There is a problem that the stability with time is poor, and in the case of a general polyvinyl alcohol-based resin, especially a highly saponified and high-viscosity product, there is a problem that the viscosity of the solution changes with time and the viscosity increases. Furthermore, with the recent high-speed operation of manufacturing and processing equipment, higher convergence has been required, and such convergence has been insufficient.

As a countermeasure, Japanese Patent Laid-Open Publication No.
In Japanese Patent Application Laid-Open No. 6-86, a glass fiber treating agent comprising polyvinyl alcohol having an average degree of polymerization of 4000 or more is disclosed in
In Japanese Patent Application Laid-Open No. 290944/1990, the content of ethylene units is 1
In Japanese Patent Application Laid-Open No. 9-30841, a glass fiber treating agent comprising a modified polyvinyl alcohol of about 24 mol% is used for a glass fiber comprising a vinyl alcohol polymer having a hydroxyalkyl group having 2 to 20 carbon atoms in a side chain. Treatment agents have each been proposed.

[0006]

However, in the above-mentioned techniques disclosed in the above publications, although a certain effect can be obtained on the convergence (adhesion) of the glass fiber, considering the recent high-speed operation of manufacturing and processing equipment, it is still insufficient. It is not satisfactory, and further improvement is required, including improvement in smoothness and flexibility.

[0007] Under such circumstances, the present invention has been developed in such a background.
It is an object of the present invention to provide a glass fiber treating agent having excellent smoothness and flexibility.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies in view of the above circumstances, and as a result, have found that a treatment for a glass fiber comprising a polyvinyl alcohol-based resin (A) and a polyalkylene glycol (B). The agent was found to meet the above-mentioned object, and the present invention was completed.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The polyvinyl alcohol-based resin (A) used in the present invention is not particularly limited as long as it is a saponified polyvinyl ester.

As such vinyl esters, vinyl formate, vinyl acetate, vinyl propionate, vinyl acetate, vinyl caprate, vinyl laurate, vinyl versatate, vinyl palmitate, vinyl pivalate, vinyl stearate and the like are used alone or in combination. Although used in combination, vinyl acetate is particularly preferable in terms of practicality. In addition, a vinyl ester copolymer resin obtained by copolymerizing a copolymerizable monomer besides the above vinyl ester in an amount of 20 mol% or less, preferably 10 mol% or less may be saponified.

Examples of copolymerizable monomers include olefins (ethylene, propylene, α-butene, α-octene, α-dodecene, α-octadecene, etc.) and unsaturated monocarboxylic acids (acrylic acid, methacrylic acid, crotonic acid). Or their esters or salts, unsaturated polycarboxylic acids (maleic acid, phthalic acid, fumaric acid, itaconic acid, etc.) or their partial or complete esters or salts or anhydrides, unsaturated sulfonic acids (ethylene sulfonic acid) , Allylsulfonic acid, methallylsulfonic acid, etc.) or salts thereof, amides (acrylamide, methacrylamide, etc.),
Nitrile (acrylonitrile, methacrylonitrile, etc.), vinyl ether, vinyl ketone, vinyl chloride and the like can be mentioned.

In the present invention, the degree of polymerization of the polyvinyl alcohol resin (A) is preferably from 100 to 5,000, more preferably from 200 to 4,000, particularly preferably from 300 to 3,000. If the degree of polymerization is less than 100, the convergence becomes poor, and if it exceeds 5,000, the permeability between single fibers becomes poor, which is not preferable.

The degree of saponification of the polyvinyl alcohol resin (A) is preferably from 70 to 100 mol%,
More preferably, it is 75 to 100 mol%. If the degree of saponification is less than 70 mol%, water solubility is lost, which is not preferable.

Further, the polyvinyl alcohol resin (A) can be acetalized, urethanized, phosphorylated, cyanoethylated, or grafted with a vinyl monomer, as long as the effects of the present invention are not impaired. .

The polyalkylene glycols (B) used in the present invention are not particularly restricted but include, for example, polyethylene glycol, polyethylene oxide, polypropylene glycol, block copolymers of ethylene glycol and propylene glycol, random copolymers, Alternatively, an alternating copolymer or the like may be mentioned, and among them, polyethylene glycol is preferably used.

The polyalkylene glycols (B)
Preferably has a weight average molecular weight of 200 to 20,000, more preferably 200 to 10,000. If the weight average molecular weight is less than 200, the effect of imparting flexibility is poor, and if it exceeds 20,000, phase separation from the polyvinyl alcohol resin (A) occurs, which is not preferable.

The glass fiber treating agent of the present invention contains the above-mentioned polyvinyl alcohol-based resin (A) and the above-mentioned polyalkylene glycols (B), and the content ratio thereof is not particularly limited. The polyalkylene glycol (B) is preferably 0.1 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the polyvinyl alcohol resin (A).
Particularly preferably, it is 0.1 to 5 parts by weight.

If the content is less than 0.1 part by weight, it is difficult to obtain the effect of imparting smoothness, and if it exceeds 20 parts by weight, the fibers may adhere to each other (blocking of the glued fibers), causing warp breakage and fluffing. Is not preferred.

The glass fiber treating agent of the present invention may further comprise a coupling agent (γ-aminopropyltriethoxysilane), if necessary, in addition to the polyvinyl alcohol resin (A) and the polyalkylene glycols (B). Silane compounds such as vinyltri (β-methoxy-ethoxy) silane), leveling agents, defoamers, surfactants, preservatives, insect repellents,
Known additives such as a rust inhibitor, a thickener, and a water resistance agent (such as a urea resin) can also be added.

Further, other ordinary film-forming agents such as starch, acrylic resin, wax, carboxymethylcellulose, nonionic, anionic or cationic synthetic resin emulsion may be used in combination as long as the effects of the present invention are not impaired. it can.

The glass fiber treating agent of the present invention thus obtained is generally used by dissolving it in water, but it can also be used in a solvent system. Examples of the type of the solvent include methanol, acetone, DMSO, ethyl acetate, methyl acetate, tetrahydrofuran, methyl ethyl ketone, and methyl cellosolve. The properties of the polyvinyl alcohol resin (A), the properties of the polyvinyl alcohol resin (A) and the polyalkylene glycol What is necessary is just to select suitably according to the content ratio of a kind (B), etc.

The preparation of the coating solution for applying the glass fiber treating agent of the present invention is not particularly limited. In short, if the water is mixed with the polyvinyl alcohol resin (A) and the polyalkylene glycols (B). Good. The concentration may be appropriately selected, but in consideration of workability and the like, 0.1.
To 40% by weight, more preferably 0.1 to 20% by weight.
% By weight.

The coating amount on the glass fiber is not particularly limited.
It is preferably applied to be 1 to 10% by weight,
More preferably, it is 0.5 to 10% by weight. If the adhesion amount is less than 0.1% by weight, convergence cannot be expected, and 10% by weight
If it exceeds, the fibers are stuck to each other, causing breakage of warp and fluffing, which is not preferable.

The coating method may be a general sizing method, that is, a method of applying to a glass fiber at an applicator portion during spinning and drying, or a method of impregnating a glass fiber product.

Thus, the glass fiber treating agent of the present invention comprises:
Since it is composed of the polyvinyl alcohol resin (A) and the polyalkylene glycols (B), it has excellent adhesiveness (bundling property), smoothness, and flexibility to glass fibers.

[0026]

The present invention will be specifically described below with reference to examples. In the examples, “parts” and “%” mean on a weight basis unless otherwise specified.

A polyvinyl alcohol resin (A) as shown below was prepared. -PVA-1: polyvinyl alcohol having a degree of polymerization of 500 and a saponification degree of 88 mol%-PVA-2: polyvinyl alcohol having a degree of polymerization of 500 and a saponification degree of 99 mol%-PVA-3: degree of polymerization of 1700 and a saponification degree of 88 mol % Polyvinyl alcohol-PVA-4: polyvinyl alcohol having a polymerization degree of 500 and a saponification degree of 80 mol%

The following polyalkylene glycols (B) were prepared. B-1: polyethylene glycol (weight average molecular weight 4
00) B-2: polyethylene glycol (weight average molecular weight 1)
000) B-3: polypropylene glycol (weight average molecular weight 4000)

Examples 1 to 8 and Comparative Examples 1 to 5 The above-mentioned polyvinyl alcohol-based resin (A) and the above-mentioned polyalkylene glycols (B) were dissolved in water at the contents shown in Table 1, and the aqueous solution concentration was 4. 5% of a glass fiber treating agent was obtained. Using such a treating agent, it was applied to glass fiber under the following conditions.

(Coating conditions) Gluing temperature 40 ° C. Gluing speed 16 m / min Drying temperature 120 ° C. Hot air drying

Adhesion (bundling) of the obtained glass fiber,
Smoothness and flexibility were evaluated as follows.

(Adhesiveness) Cut fluff length One of the glass fibers (30 cm) subjected to the gluing treatment is fixed, a weight having a load of 100 g is hung on the other, and the weight is separated from the glass fiber fixing portion by 10 cm, and the gravity is removed. When the glass fiber was dropped and the glass fiber was cut, the fluff length (cm) of the cut portion was measured.

Conjugation Force A glass fiber that has been glued is loaded with a load of 100 g / 10 at an angle of 145 using a TM type conjugation degree tester (manufactured by Matsui Seiki Co., Ltd.).
The degree of convergence of the glass fibers at the time of reciprocating frictional movement 25 times was observed and evaluated in nine grades of first to ninth grades. The higher the grade, the better the embracing power.

(Smoothness) Friction coefficient The dynamic friction coefficient between the pasted glass fibers was measured with a μ meter (manufactured by Eiko Co.).

(Flexibility) Bending hardness Twenty pieces of glass fibers (2 cm) that have been glued are arranged at equal intervals on a plane (pseudo-woven fabric), both ends are chucked, one is fixed, and the other is 90 degrees to the right. After bending, 180 to the left
Force after returning to original position after bending (gf · cm /
cm). Table 2 shows the evaluation results of the examples and the comparative examples.

[Table 1] Polyvinyl alcohol Polyalkylene glycols Coating resin (A) (B) Kind Content Kind Content (%) Example 1 PVA-1 100 B-1 1 2.7 # 2 PVA- 1 100 B-1 3 2.7 3 PVA-1 100 B-1 5 2.7 4 PVA-2 100 B-1 3 2.7 5 PVA-3 100 B-1 3 3.0 6 PVA-4 100 B-1 3 2.8〃7 PVA-1 100 B-2 32.7〃8 PVA-1 100 B-3 3 2.7 Comparative Example 1 PVA-1 100 ---- 2.7 〃 2 PVA-2 100 ----- 2.7 〃 3 PVA-3 100 ----- 3.0 〃 4 PVA-4 100 ----- 2.8 ５ 5 PVA-5 100 ----- 3.0

Note) PVA-5 is a hydroxyalkyl-modified polyvinyl alcohol modified with 3-buten-1-ol, having a modification amount of 5 mol%, a polymerization degree of 600 and a saponification degree of 99 mol%.

[Table 2] Adhesive smoothness Flexible cutting fluff length Entrapment force Friction coefficient Bending hardness (cm) (grade) (gf · cm / cm) Example 1 0.5 6 0.40 96 × 10 ^{− 4} 〃 2 0.45 0.37 78 × 10 ^-4 ３ 3 0.45 0.35 60 × 10 ^-4 ４ ⁴ 0.57 0.3999 99 × 10 ^-4 ５ 5 0.350 .38 114 × 10 ^-4 〃6 0.35 0.37 72 × 10 ^-4 ７7 0.45 0.38 99 × 10 ^-4 〃8 0.45 0.39 104 × 10 ^-4 Example 1 0.57 0.44 234 × 10 ^-4 〃2 0.68 0.46 260 × 10 ^-4 〃3 0.46 0.44 288 × 10 ^-4 ４40.460. 44 195 × 10 ^-4 〃 5 0.46 0.44 250 × 10 ^-4

[0039]

Since the glass fiber treating agent of the present invention comprises a polyvinyl alcohol-based resin (A) and a polyalkylene glycol (B), it has very low adhesion, smoothness and flexibility to glass fibers. It shows an excellent effect. In addition, the present invention can provide excellent glass fiber as an electronic material component (precision material product), a resin sheet reinforcing material, and a cement product reinforcing material, and has very high industrial value.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // D06M 101: 00 C03C 25/02 NF term (Reference) 4G060 BA01 BC01 BD05 BD15 CB05 4J002 BE02W BE03W CH01X CH02X GH02 4L033 AA09 AB01 AC11 AC12 CA29 CA48

Claims (3)

[Claims] 1. A glass fiber treating agent comprising a polyvinyl alcohol resin (A) and a polyalkylene glycol (B). 2. The glass fiber treating agent according to claim 1, wherein the degree of polymerization of the polyvinyl alcohol resin (A) is from 100 to 5,000, and the degree of saponification is from 70 to 100 mol%. 3. Polyvinyl alcohol resin (A) 10
0 parts by weight of polyalkylene glycols (B)
The glass fiber treating agent according to claim 1 or 2, comprising 0.1 to 20 parts by weight.