JPS6047387B2 - fiber sizing agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a sizing agent for fibers, particularly a sizing agent that effectively exhibits alkali resistance for fibers used as reinforcing materials for cementitious materials.

Glass fibers are usually classified into short fibers and long fibers. Of these, the long fibers are usually drawn from a platinum alloy bushing with 400 to 200 orifices, drawn to form a group of filaments, and then treated with a sizing agent. It is manufactured by applying a sizing agent to form a strand, winding it up, and curing the sizing agent.

Depending on the application, sizing agents can be used in textiles, plastics, rubber,
Sizing agents suitable for reinforcing materials such as cementitious materials have been developed. Among these, phenolic resin,
Products based on resins such as vinyl acetate resin, polyvinyl alcohol resin, and furan resin, or using these resins and adding coupling agents, lubricants, dispersants, metal salts to improve alkali resistance, alumina sol, silica sol, etc. It is being developed.

However, among these surface treatment agents, there are few that can be used as sizing agents, and they have good adhesion to cementitious materials.
It is also desired to develop a sizing agent that can effectively improve alkali resistance. In view of this, the present inventor has conducted various studies and examinations with the aim of finding a sizing agent that can effectively improve alkali resistance and maintain its effect. It has been found that the above object can be achieved by adding specific additives to the.

Thus, the present invention provides an ethylene/vinyl acetate copolymer,
The object of the present invention is to provide a fiber sizing agent comprising a lignin sulfonate added to a mixed emulsion with a phenolic resin.

The phenolic resin used in the present invention may literally be any phenolic resin, but the use of resol resin, which is an intermediate thereof, is particularly effective in maintaining alkali resistance.

Also, the concentration of the mixed emulsion used is 50
Approximately 500 y/' is appropriate.

If the emulsion concentration is less than the above range, the coating of the resin on the fibers will be rough and it will be difficult to obtain alkali resistance.On the other hand, if it exceeds the above range, the strands will come apart in a cake state and roping may occur. Both are unfavorable because there is a risk that workability, compatibility with cementitious materials, and moldability will be extremely deteriorated. Among these emulsion concentrations, when adopting an emulsion concentration of 100 to 300 y/e, there is no problem with the condition of the cake, workability of roping, moldability with cementitious materials, etc., and the alkali resistance is significantly improved. Particularly preferred. In addition, in the present invention, ethylene
The mixing ratio of vinyl acetate copolymer and phenol resin is ethylene/vinyl acetate copolymer 9.8 to 0 in terms of solid content.
．． 2: Phenol resin 0.2 to 9.8 is suitable.

If the mixing ratio deviates from the above-mentioned range, problems will occur in the condition of the cake, workability of roping, moldability with cementitious materials, alkali resistance, etc., as described above, and therefore it is not preferable.

And within the above range, according to the above indication, 9.0 to 5.
When adopting 5:1.0 to 4.5, the resin coverage on the strands becomes dense, the alkali resistance improves,
It is particularly preferred since it has good roping workability and moldability with cementitious materials.

The ethylene/vinyl acetate copolymer used in the present invention is
The content of vinyl acetate is 10 to 4%, especially 15 to 35%
Copolymers containing % by weight are preferred.

Also, ligninsulfonic acid used in the present invention. The salt is
Alkali metal or alkaline earth metal salts of ligninsulfonic acid are used. The appropriate amount of the lignin sulfonate to be used is 0.1 to 7 weight percent, preferably 5 to 5 weight percent, based on the phenol resin.

When the amount used is less than 0.1% by weight, it is substantially difficult to achieve the desired effect of maintaining alkali resistance,
On the other hand, if the amount exceeds 7%, the workability of roping and the formability with cementitious materials will be affected, and no further improvement can be expected in terms of durability of alkali resistance. I also don't like it. Furthermore, in the present invention, other than the above-mentioned components, for example, softening agents such as alkylimidazole derivatives, peragonic acid amide, tetraethylenepentamine derivatives, vinyl ethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxy Crosslinking agents such as silane, polyethylene glycol, antistatic agents such as ammonium chloride, acetic acid,
PH adjusters such as hydrochloric acid and aqueous ammonia can be used as long as they do not impede the purpose of the present invention.

The amount used is strictly determined by the materials used, but is generally preferably 3% by weight or less. The sizing agent thus obtained is applied to the fibers by an appropriate means.

Taking glass fiber as an example, a glass raw material with a desired composition is melted, flowed out through a number of orifices in a platinum alloy bushing, drawn to form a glass filament, and this filament is coated using a roller method. The fibers are brought into contact with a winder, coated with the sizing agent of the present invention, bundled into strands, passed through a traverser, and wound onto a winder.

Next, the wound fiber is heated for about 1 hour, usually at 120 to 140°C, to harden the sizing agent. As the fibers used in the present invention, inorganic fibers such as glass fibers, rock wool, and asbestos are widely used, and among these, good results can be obtained by employing glass fibers, especially alkali-resistant glass fibers.

Such alkali-resistant fibers include SlO25O-70, ZrO21O-22, preferably 10-30 in total of alkali metal oxides and alkaline earth metal oxides, other oxides or halogens, respectively expressed in weight%. 0 monsters etc.
It is preferable to adopt .about.20. By doing so,
High alkali resistance and durability can be obtained. The fibers surface-treated with the sizing agent of the present invention are mainly used for reinforcing cementitious materials, but they can also be used as members that come into contact with alkaline materials. The cementitious substances used in the present invention include, for example, Bortland cement, alumina cement, magnesia cement, gypsum, lime, calcium silicate raw materials, etc., and various additives such as sand, gravel, aggregate, asbestos, valve, etc. In particular, the sizing agent of the present invention has an alkali-resistant effect and a long-lasting effect on Boltland cement-based cementitious materials, which are traditionally highly alkaline and have been pointed out to deteriorate the strength of glass fiber reinforcement. The gender is remarkable. Next, the present invention will be explained by examples.

In addition, in the following examples, SlO25 is
8, ZrO2l5, CaO5, Na2Ol8, Ll. O
3. A sizing agent according to the present invention shown above was applied to 204 glass filaments having a composition of Na2SO4L and a fiber diameter of 13μ, and the sizing agent was wound into a single strand and dried.

Comparative example resol resin emulsion (Plyoven l'ID
43O2) 2% γ-aminopropyltriethoxysilane (A-1100)
0.3 Stearic acid ◆ Tetraethylenepentamine (Sofnon HGl8O)
0.8J polyethylene glycol (PG2OOO
) 0.1 acetic acid (adjusted to pH 5.5) ion exchange water
Remaining Example 1 Ply oven TD43O22 Heel weight %2 Calcium lignin sulfonate 2.8N-β(aminoethyl)γ-aminopropyltriethoxysilane (All2O)
0.3 Sophnon HGl8OO. 8NFl4ClO.
l2 Acetic acid (adjusted to pH 5.0) Ion exchange water
Remaining Example 2 Resole resin emulsion (BKUA237O)
2% heel volume! Calcium lignin sulfonate
8.1β(3,4epoxycyclohexy)ethyltrimexysilane (Al86) 0.4
Cabrylic acid ◆Tetraethylpentamine (chemitylene SGF2) 0.9.

Acrylic modified resin emulsion (Sevian A46753
) 0.1 acetic acid (adjusted to pH 4.5) ion-exchanged water Remaining example 3 resol resin emulsion (IAlOO7)
2% calcium lignin sulfonate 13.5γ-methacryloxypropyltrimethoxysilane (Al74)
0.4 lubricant (Cirr'AsO
ll85A) 1PG2
0000.1 Acetic acid (adjusted to pH 3.5) Ion exchange water Remaining 4 Example 4
Plyoven TD43O2l 5% by weight ethylene/vinyl acetate copolymer emulsion (Movinyl 181E)
15 Sodium lignin sulfonate
3 Vinyl Tris(β-methoxyethoxy)silane (Al72) 0.4Ci
rr'AsOll85AO. 8NH4ClO. l acetic acid (
Adjusted to pH 4.5) Ion exchange water
Residue Example 5BKUA237015% by weight acrylic resin emulsion (Primal HAl6) 15 Calcium lignin sulfonate 3A1720.5 Tetraethylenepentamine (Cir [″AsOll2O)
0.8 Polyethylene glycol (PGlOOOO) 0.1 Acetic acid (
Adjusted to pH5.5) Ion exchange water
Residual Example 6 IA1007 15% by weight Vinyl acetate/tertiary synthesis saturated carboxylic acid vinyl ester (V Latex SAH) 15 Sodium lignin sulfonate 3A-11000.5Cirr"As
OIl85AO. 7PG2OOOO. l acetic acid (PH5.
(adjusted to O) ion exchange water
Remaining Example 7 IA1007 15% by weight Epoxy resin emulsion (EP-601) 15 Magnesium lignin sulfonate 3A11000.4 Chemitylene SG
F2O. 8N HlClO. l Acetic acid (adjusted to pH5.O)
Ion exchange water Remaining example 8
Plyoven TD43O 29% by weight vinyl acetate and ethylene copolymer emulsion (EVA-AD5)
21 Calcium lignin sulfonate 3A1740・4Sofnon HGl8OO
．． 8 Sebian A46753O. l Acetic acid (adjusted to pH 5.5) Ion exchange water Remaining Example 9
Plyoven TD43O22l weight%EVA-AD
59 Calcium ligninsulfonate 4A-110
00.4 Chemitylene SGF2O. 8-NH4ClO. l Acetic acid (adjusted to pH 5.0) Ion exchange water Remaining example 1
0-ply Orven TD43O2l 5% by weight - Movinyl 181E3.5 Calcium lignin sulfonate
0.2A-11000.4 Chemitylene SGF2O.
8PGllOOOO. l Acetic acid (adjusted to pH 5.0) Ion exchange water Residue Example 11 Ply oven 'IT) 43026% by weight Movinyl 18
1E14 Sodium lignin sulfonate 1
A-11000.4 Chemitylene SGF2O. 8NHiC
lO. l Acetic acid (adjusted to pH 5.0), ion-exchanged water
Residue Example 12 Ply Owen TD43O224% by weight Movinyl 181E5 Weight% Sodium ligninsulfonate 4.8A-1
1000.4 Chemitylene SGF2l. 5NI: IbClO. 2 Acetic acid (adjusted to pH5.O)

Claims (1)

[Claims] 1. A fiber sizing agent made by adding lignin sulfonate to a mixed emulsion of an ethylene/vinyl acetate copolymer and a phenol resin. 2. The sizing agent according to claim 1, wherein the mixed emulsion of the ethylene/vinyl acetate copolymer and the phenol resin has a concentration of 50 to 500 g/l. 3. Claim 1: The mixing ratio of the ethylene/vinyl acetate copolymer and the phenol resin is 9.8 to 0.2 for the former and 0.2 to 9.8 for the latter in terms of solid content ratio. A focusing agent. 4. The sizing agent according to claim 1, wherein the lignin sulfonate is an alkali metal salt or alkaline earth metal salt of lignin sulfonic acid. 5. The sizing agent according to claim 1, wherein the amount of the lignin sulfonate used is 0.1 to 70% by weight based on the phenol resin.