JPS5950052A - Method for providing hydrophilic property to glass and glass fiber - Google Patents

Abstract

PURPOSE:To obtain glass fibers having superior hydrophilic property and water retentivity, by treating glass and glass fibers with a system contg. a polymer of an N-contg. compound having a specified structure to make the glass wettable with water. CONSTITUTION:Glass and glass fibers are treated with an aqueous soln. of a hydrophilic property providing agent contg. >=1 kind of compound represented by the general formula (where each of R1 and R2 is H, alkyl, alkyl contg. a functional group or aralkyl, X is Cl or Br, and M is the residue of a vinyl monomer), e.g., diallyldimethyl-ammonium chloride. Air drying and drying under heating are then carried out. The amount of the agent to be stuck is about 0.01-10wt% of the amount of the glass fibers. Since the agent has positive charges, it bonds firmly to the surfaces of the glass fibers by ionic bond, so the hydrophilic property, dispersibility and water retentivity of the glass fibers can be improved.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to glass and glass 11! This invention relates to a method for making fiber hydrophilic.

Traditionally, asbestos has been used in various applications such as asbestos-cement boards, but due to sanitary and carcinogenic issues, legal regulations require alternatives.

One of the alternatives is glass fiber. However, glass fiber lacks the properties required for papermaking methods, such as hydrophilicity, water retention, and prevention of solid content that asbestos possesses.

As a result of intensive research into treatment methods for glass fibers that have properties similar to those of asbestos, the present inventors discovered a hydrophilic agent that makes glass hydrophilic, and by applying this to glass fibers, it becomes easier to wet the glass with water. Glass 11 has good dispersibility and excellent water retention! It was successful in providing fiber. Here, the glass fibers include inorganic fibers such as ceramic fibers, rock wool, and slag wool, which are analogs thereof, in addition to E glass fibers and alkali-resistant glass fibers.

That is, the present inventors discovered a compound (I) represented by the following general formula (r) (where R, R, is a hydrogen atom, an alkyl group, an aralkyl group, a functional group-containing alkyl group, or an aralxy-17 'Zumer residue 1m is an arbitrary integer, n is zero or an arbitrary integer). This is what I discovered.

The compound represented by the general formula +1) used in the present invention (
(hereinafter referred to as a hydrophilic agent) is synthesized as follows.

That is, diallyl 7 represented by the following general formula (It)
Organic solvents such as methyl alcohol, ethyl alcohol, acetone, dimethyl sulfoxide,
In water or a water-containing organic solvent, in the presence of an organic radical polymerization initiator such as l-butyl hydroperoxide or azobisisobutyronitrile, or an inorganic radical polymerization initiator such as ammonium persulfate, or under irradiation with radiation. It can be obtained by polymerization (when ?L is zero) or by copolymerizing a suitable vinyl monomer (button) (when 9 is an arbitrary integer).

R and )2 (1) (However, R1 + R2 * X * M * Ill #
? L is the same as above. ) diallylamine derivative (
11) alkyl group and or aralkyl group (R1),
(Rr) is preferably a lower alkyl group and/or a lower aralkyl group, such as a methyl group.

Ethyl group, propyl group, butyl group, benzyl group.

Examples include 4-methylbenzyl group. Also, (R1
), (horse)K Examples of the functional groups included are hydroxyl group, carboxyl group, and carbamoyl group.

Carboxylic acid alkyl group, nitrile group, formyl group.

Examples include sulfuric acid groups.

Vinyl monomers used in the synthesis of copolymers with cin'lylamine derivatives (if) include, for example, (meth)acrylic acid, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-butoxymethyl-(
meth)acrylamide, methyl(meth)acrylate, (
ethyl meth)acrylate, hydroxyethyl (meth)acrylic acid, (meth)acryloyloxyelalkyl ammonium halide), r-(meth)acryloyloxy-β-hydroxypropyl trialkylammonium halide, acrylonitrile , styrene, vinyl acetate, sulfur dioxide, etc.

The (, +-) of the hydrophilizing agent (1) used in the present invention represents the average degree of polymerization, and is applied to hydrophilizing. be done.

Specific examples of the hydrophilizing agent (I) used in the present invention include H C,H,)l C,H,HC,H,H CH,CHs CH3C1l(3 sing PL21.;6 MlHOCH,C
H, CH, CH, OH CH, CH.

CH, CH.

CH, CCH, CH, 0H CH.

／　　＼ CH8CH.

C horse CH, CH.

CH, CH.

Shifil　　　υMl CH.

／　　＼ CH, CH.

HOCH,CH,CH,OR,0H HOCH,CH,CH,CH,0H HOC)(,CI(,CH,CH,0HCIHs
H C Mountain H NCCH,CH,H HOCH,CH,HC,Hllc,HOR,CH,CH,0H C)(,CH,CH,0)I CH,CH,CH,C0NH.

etc.

The hydrophilic agent of the present invention has a hydrophilic effect when applied to glass and glass fibers, but is it suitable for glass fibers? Is it possible to apply a hydrophilic agent solution? It is something that is applied or attached to glass fibers. For example, in a sizing agent applying device used in a normal glass-fiber spinning process, a hydrophilic agent is mixed into the sizing agent, and then the hydrophilic agent is mixed with the sizing agent. This is impregnated and then baked in the next step, the drying step. The amount of hydrophilic agent attached to the glass fiber is 0.01 to 1
0% by weight, from a performance and economic standpoint 0.1~
4% by weight is preferred.

The hydrophilizing mechanism of the hydrophilic agent is thought to be as follows. That is, it is known that the surface of normal glass L# male is negatively charged, and on the other hand, the highly hydrophilic agent of the present invention has a positive charge. Therefore, it is thought that the surface of the glass fiber is strongly bonded to the surface of the glass fiber through ionic bonding. This is thought to improve the hydrophilic dispersibility and water retention of the glass fibers.

Therefore, glass NI fibers treated with a hydrophilic agent can be advantageously used, for example, in the field of paper making such as glass paper, and as an alternative to asbestos in the production of asbestos cement boards, gypsum slag boards, pulp cement boards, and the like.

Furthermore, the invention can be applied not only to crow fibers but also to glass plates. Water droplets on a glass plate treated with the hydrophilic agent of the present invention? When a droplet falls, it immediately spreads out and disappears instantly.

The hydrophilicity of the hydrophilic glass of the present invention is semi-permanent, as is clear from the above mechanism of hydrophilicity expression.

Is the effect of the hydrophilic agent of the present invention on glass fiber sedimentation rate tests and water droplets on glass plates? falling, as evidenced by its small contact angle. In the sedimentation rate test, up to 500 cc of water or an aqueous solution such as polyethylene oxide aqueous solution, carboxymethyl cellulose aqueous solution, cement supernatant liquid, etc. is placed in a 500 cc graduated cylinder, and glass fibers (chopped) treated with a water retention agent are placed in the cylinder. Strands) and glass fibers that are not treated with hydrophilic agents? Add 50
The settling time from 4oocc to 100cc in a 0cc graduated cylinder can be measured.

In this case, the glass fibers treated with the hydrophilic agent are well compatible with water, each glass fiber is well dispersed, and the settling time is longer than that of the glass fibers not treated with the hydrophilic agent.

Examples will be described below.

Example 1 0.1% of a homopolymer of diallyldimethylammonium chloride (hereinafter referred to as compound A), 0.
5%, 2.0% water bath liquid? Glass fiber threads (number of collected fibers: 200) were prepared and collected in these three types of water bath solutions.

19~20μ)? After soaking and air drying for 1 day, the samples were heated and dried in a hot air dryer at 110° C. for 1 hour.

These strands were cut into shiso chopped strands with a length of 13 IIm, and two sedimentation rate tests were conducted. Sedimentation rate test is 10% of polyethylene oxide (pEo)
PP aqueous solution? using the method detailed above, 5
What is the result of measuring the sedimentation rate of the above chopped strand in a measuring cylinder of 0Qcc? Shown in Table 1. For comparison, we conducted a sedimentation rate test on chopped glass fiber strands that had only been subjected to water collection but not treated with a water softening agent. This is shown in a comparative example.

In Table 1, the amount of adhesion when treated with a 2% aqueous solution of compound (A) was 2.2%.

Example 2 0.1% and 0.5% of a copolymer consisting of about 50 mol% diallyldimethylammonium chloride and about 50 mol% sulfur dioxide (hereinafter referred to as Y compound part B)
, 2.0% water bath liquid? The chopped strands for three types of tests were prepared and treated in the same manner as in Example 1.
Obtained. In addition, Example 1 except that the cement supernatant liquid was used instead of the polyethylene oxide aqueous solution in the sedimentation rate test.
In the same way, I begged for the exam.

Results obtained? Shown in Table 2.

For comparison, chopped strands of glass #fiber with water condensation and no treatment with a hydrophilic agent were prepared.
What are the results of the sedimentation test? This is shown in a comparative example.

Table 2 Example 3 Glass plate? After washing with a chromic acid mixture, a 2% aqueous solution of the compound (obtained in Example 1) was applied to this glass plate, and this was heated and dried in a hot air dryer at 110°C for 1 hour to remove the hydrophilic agent. A glass plate with Obtained. When a water droplet Y falls on this glass, the water droplet spreads immediately, and the contact angle is less than 5°, which is 0. On the other hand, the hydrophilic agent? On the uncoated glass plate, water droplets do not spread even if you go downstairs.
The water remained in a spherical shape for a long time.

As described above, the glass or glass fiber treated with the hydrophilizing agent of the present invention has poor hydrophilicity, and the glass fI
In the case of N fiber, it can be advantageously used as a substitute for asbestos.

Claims (1)

[Scope of Claims] Compound CI (.
is a chlorine atom or a bromine atom, M is a vinyl monomer residue, L is an arbitrary integer, and tL is zero or an arbitrary integer. 1. A method for making glass and glass fibers hydrophilic, the method comprising treating with a system containing at least one of the following.