JPS5895629A - Making glass and glass fiber hydrophilic - Google Patents

Abstract

PURPOSE:To provide semipermanently glass and glass fibers with hydrophilic nature, by treating glass and glass fibers with a mixed system comprising a specific compound and a water-soluble high polymer containing OH group and/or carboxyl group. CONSTITUTION:A compound shown by the formula III (M is vinyl monomer residue; n is 0 or arbitrary integer; 10<=m+n<=200) obtained by subjecting silane compound shown by the formulaI(R1 is alkyl; R2 is alkylene; R3 is hydroxymethyl, or alkoxymethyl) to which 3 alkoxy groups and one mercapto group- containing organic group are bonded and an acrylamide drivative shown by the formula II (m is arbitrary integer) or it and a vinyl monomer to radical addition reaction is blended with a water-soluble high polymer (e.g., starch) containing OH group and/or carboxyl group to give a hydrophilic agent. Glass and glass fibers are immersed in an aqueous solution of the hydrophilic agent so that 0.01-10wt% hydrophilic agent is attached to the glass and glass fibers, which are dried under heating and baked.

Description

DETAILED DESCRIPTION OF THE INVENTION Zero lead light is a threshold method for making glass and glass fibers hydrophilic.

Traditionally, stone has been used for various products such as 15 nishiki cement boards, but due to hygiene and carcinogenic properties, it has an interlayer.
Substitute products are required by laws and regulations.

Glass fiber is one of the 5#I alternative crystals. However, glass fiber has hydrophilic and water-retaining properties similar to that of stone.
It lacks the characteristics necessary for the papermaking method, such as prevention of spillage and solid matter.

The inventors of the present invention have conducted extensive research on a method for treating glass fibers to have properties similar to those of asbestos, and as a result, they have discovered a hydrophilic agent that makes Dallas hydrophilic, and succeeded in supplying glass fibers with this agent.

That is, the present inventors have developed a compound represented by the following general formula (11) (where Peng is an alkyl group and Tokki is an alkylene group.

Dimethyl group or alkoxymethyl group, M
is a mixed system of at least one of the following and at least 418 of a hydroxyl group-containing and/or carboxyl group-containing water** polymer. It has been found that by treating glass and glass fibers, the intended purpose is achieved.

, Honji WAK'W! The general formula used (the compound represented by 11 is hereinafter referred to as a hydrophilizing agent) is a parent compound,
It is synthesized in the next step 5. That is, first, when the sieve is zero, a schiller compound (11) in which five alkoxy groups represented by the following general formula and one organic group containing a mercap F group is combined with an acrylamide compound represented by the general formula (Shu). It is obtained by a radical addition reaction with a derivative in the presence of an appropriate radical polymerization initiator.

(However, 〇 means an alkyl group, chicken means an alkylene group, - means a human dioxymethyl group or an alkoxymethyl group, and 〇 means an arbitrary integer) Alkylene group (8) of compound (i)
is preferably a lower alkylene group, such as an ethylene group, a propylene group, a butylene group, a pentamethylene group, or a hexamethylene group. The octahedron in chemical compound (2) represents a dotetraxoxymethyl group or an alkoxymethyl group, and the alkoxymethyl group is preferably a lower alkoxymethyl group, such as a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a methoxymethyl group, etc. Examples include methyl group.

The addition reaction is carried out in water, a water-containing organic solvent, or an organic solvent.
Bulbyl alcohol, butyl alcohol, dioxane,
Examples include tesilahydrofuran, benzene, toluene, xylene, dimethylformamide, dimethylaceamide, dimethylsulfonide, N-methylbiridone, and mixed solvents thereof.

Preferred examples of organic solvents used as the water-containing organic solvent include methyl alcohol, ethyl alcohol, dioxane, dimethylformamide, dimethyl sulfoquinide, and solvents with lacquer properties.

The initiator used in the addition reaction is preferably an organic peroxide that is usually used as a radical polymerization agent, such as cumene, gastric peroxide, Preferred are redox polymerization initiators such as ruberoxide, benzoyl peroxide, and azobisisobutyronitrile, such as hydrogen peroxide-ferrous sulfate, ammonium persulfate-sodium bisulfite, and potassium persulfate-bisulfite. Soda, potassium persulfate (β-dimethylammonium chloride 9J/), and the like. The temperature and time of the addition reaction are determined by the initiator IIIK.
Therefore, organic peroxides generally require higher temperatures, but for example, benzoyl peroxide requires a temperature of 80°C at 80°C.
The addition reaction ends at the threshold strength. Further, in the case of a redox initiator, the reaction can be carried out in several hours at a temperature of room temperature to 50°C. The amount of the initiator used is several % (wt.
) or less is sufficient, and usually α1% to 2% is am.

The adduct of compound (1) and N-alco-im-dimethylacrylate in the case where the audience represented by the general formula (!l) used in the present invention is zero, is compound (1) under KN-alkaline conditions. Addition of formaldehyde to the amide group fi-
It is also possible to form an alkoxymethyl group in a so-called polymer reaction by treating with an excess of alcohol in the presence of an acidic catalyst such as p-toluenesulfonic acid.

The hydrophilic agent obtained by the above Kaii method has the general formula (1
) of the wood-loving agent represented by 55, S is zero, but when rattan is an integer, the general formula (vinyl basket represented by M of Il)! - contains residues. That is, in this case, Compound (1) is a K acrylamide derivative (11 copolymerized with a vinyl monomer).

When collecting hundreds of long glass fibers of 10 μm to 20 μm and processing them into a strand, you can use Vinyl Mono to check the strand's cohesiveness and hardness, in addition to controlling the strand KIA* properties! Copolymerized hydrophilic agents with - are effective, and recommended vinyl polymers for this purpose include acrylamide, vinyl acetate, atarynitrile, styrene, methyl (meth)atalate, (meth) Examples include acrylic acid and sodium (meth)acrylate.

Book JillKI! The hydrophilic agent used (I>) represents the average degree of polymerization, and its value is the ratio of the sum of the moles of the compound (button and vinyl basket) to the mole number of compound (1). A specific example of the hydrophilizing agent (Il) used in the present invention is (
G%O), 811DQ)%G;)4C crosspiece 8(C%CH-
),)iCαKantōC to QC, Tokinato can be raised.

On the other hand, specific examples of water-soluble polymers containing hydroxyl groups and/or carxyl groups that can be used in combination with the hydrophilizing agent (I) of the present invention include starches, natural gums (such as laggant gum, Appyago 5, etc.), carboxyl Ethyl starch.

Carboxyethyl starch, poly(meth)acrylic daft starch, polyacrylic daft starch, and tokidiethyl starch, dialdehyde starch,
Cyclodextrin.

Calf-xymethyl cellulose, todo-shimei diethyl cellulose, sodium alginate, polyvinyl acetate partial saponification, polyvinyl alcohol, polyvinyl alcohol!
Leic acid co-heavy metal, sodium polyatarylate.

Hereinafter, the base system of the hydrophilic agent (I) used in this Example 14 and the water-soluble polymer containing a hydroxyl group and/or a calf-xyl group will be referred to as a composite hydrophilic agent.

The composite hydrophilizing agent of the present invention has hydrophilic properties when applied to glass and glass fibers. When making glass fibers hydrophilic, the composite hydrophilizing agent is melted into a casing of 11af1 of iron.
A cloth or something that is impregnated and attached to c1.1 For example, in a sizing agent applying device used in ordinary glass fiber spinning 11K, a composite hydrophilic agent is mixed into the sizing agent, and the composite hydrophilic agent is impregnated together with the sizing agent. This is then baked in the next heating and drying process.5. The amount of the hydrophilic agent attached to the glass fiber is 1 to 1% by weight, and preferably 4 to 4% by weight from the performance and economical standpoints.

The lignophilization mechanism of the 1sha hydrophilic agent is included in it (11
When the wood-loving agent represented by the formula is hydrolyzed in an aqueous solution, the alkoxy group bonded to the silicon atom becomes silano,
Glass fiber 8. The -OH group dehydrates and condenses during heating and drying to form a covalent bond with the glass fiber. On the other hand, the polyacrylic acid derivative residue becomes hydrophilic due to hydrogen feeding, so that one glass fiber It is thought that hydrophilicity, dispersibility and water retention are improved. Furthermore, the lyacrylate derivative residue of the wood-loving agent has an N-hydroxymethyl group (-NO) or an N-al;oxymethyl group (-
NCH,0ReR contains an alkyl group), and these functional groups react with the above-mentioned hydroxyl group and/or carbodP/Af group water-soluble polymer contained in the composite hydrophilic agent during heat drying. By dehydration or dealcoholization,
-NcHsO- water-soluble polymer, or -N041I0
It is thought that the bond of 0c-water-soluble polymer is generated. In other words, the structure is thought to be one in which a water-based polymer is grafted onto a hydrophilic agent, and the result is a structure in which a water-soluble polymer is grafted onto glass fibers via a hydrophilic agent. Therefore, it is considered that the hydrophilic dispersibility and water retention properties of the glass fibers are further improved.

Therefore, it is necessary to receive a composite hydrophilic agent! The twisted glass fibers can be advantageously applied 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 boards, etc.

Furthermore, the present invention can be applied not only to glass fibers, but also to steel plates. When water droplets are dropped on a glass plate treated with the composite hydrophilic agent of the present invention, the water droplets disappear instantly.

Glass treated with the composite hydrophilic agent of the present invention has semi-permanent hydrophilicity, as estimated from the above-mentioned hydrophilicity development mechanism.

The effect of the composite lignophilizing agent of the present invention was demonstrated by a glass fiber sedimentation rate test and by dropping water droplets on a glass plate, and the contact angle was small (11).
It is proven by this. In the sedimentation rate test, up to 500 cc of water or water** system, such as polyethylene oxide (PEO) water S* or carboxymethyl cellulose (CMC) water S*, is placed in a 50 Ct measuring cylinder, and K11 is hydrophilized in it. Glass fibers treated with the compound hydrophilic agent (chopped strands) and glass fibers not treated with the composite hydrophilic agent were added, and 40
Measure the settling time from mouth CC to 10Occ. In this case, the glass fiber treated with the composite hydrophilic agent is well adapted to water, and its sedimentation time is longer than that of the fiber that is not treated with the composite hydrophilic agent.

Examples of Ii theory will be explained below.

Reference example! Dioquinane 15OCCKr-Mercapdobutylsilymethoxysilane 2.4°C% N-butoxymethylacrylamide 5t' Is A solution in which benzoyl peroxide α5# was dissolved was heated and stirred at ao"c for 8 hours. From the analysis of the reaction mixture. , this one has about 20 dimethyl aryl groups added in N-buto (CH,O), 810H.

This product was confirmed to be diochitene mii (referred to as (2)).

Reference Example 2 Diochitin 1soo: Kr-mercagutogoupyrtrimethoxysilane L4t% N-butomedium dimethylacrylic acid it 4#, vinyl acetate tip, benzoyl peroxide a5p dissolved in a solution was heated at 80°C for 8 hours. Analysis of the heated and stirred reaction mixture revealed that this product contained about 20@1s of N-butoxymethylacrylado and #1s of vinyl acetate.
It was confirmed that the substance was diquinane Minatojo (hereinafter referred to as ni) having 0)a added to α.

Reference books & water 10, ccKr-mercapdobu biltrimethoxysilane L4f, N-human W now dimethyl axyladende 41
1. Acrylic acid 1111t was dissolved, and after adding persulfurized Calicum 127# and sodium bisulfite (L11#), -shu was heated and stirred at 40°C for 3 hours at 40°C. Approximately 5 acryl urethanes, acryl urethane, and the compound obtained in Reference Example (1) were added to the dioquine S solution and diethyl cellulose () iEc) and water to form a compound. α5% and) iECg, 1%, compound (A+t
o% and hECn, 1%, compound (Ala C1%
1) A solution containing 1% of E-Ca was prepared. In addition, a dioxane solution vchEC of the compound (b) obtained in Reference Example (2) and water were added to form a compound @2.0%).
A solution containing IEC (L1%) was prepared. Furthermore, water and carbo-dimethyl cellulose (CMC) were added to the aqueous solution of the metal compound (0) obtained in Reference Example (5) to prepare the compound (01).
5% and CMC (12%, 5zos and CMC (L
2%, compound @1155. Aqueous solutions containing a% and CMC (L2%) were prepared respectively.These 7 types of *tK water focused s'ps fiber systems (number of bundles: 200, fiber diameter: 1!
~2111 voices) were immersed, air-dried for one day, and heated in a hot air dryer at 130°C for 1 hour to burn-in the glass fiber-based metal hydrophilic agent. 1311 of these things
The sample was cut to a size of 1 to 1, and a sedimentation rate test was conducted. Sedimentation rate test 11★Lupo dimethyl 7-luce (CMC 12% 1% viscosity at ℃ 15
-! Using a 50 ppm aqueous solution of -C1 (5Ocp), the sedimentation rate of the above-mentioned tipped stone was kept constant in a 50-mouth CC measuring cylinder using the method detailed above.
As shown in the table, for comparison purposes, the results of a sedimentation rate test performed on chipped glass fibers that were only water concentrated and not treated with a composite hydrophilic agent are shown as comparative examples.

Table 1: When wearing water S*''cm containing hydrophilic agent (Q (L5%) and CMC (L2%), the adhesion amount of the hydrophilic agent is 12%.
Met.

*The 11sHz iIy glass plate was cleaned with a chromic acid maple casing, and the hydrophilic agent (010% and CMC1 obtained from the glass [K reference example (i%l)
2% of water SII was applied, and this was heated in a hot air dryer at 130° C. for 1 hour to obtain an S-cus board decorated with an optional hydrophilic agent. When a drop of water was applied to this stX plate, the water droplet turned downward and the contact angle was C or less.

On the other hand, the glass plate that was not coated with the Group II hydrophilic agent did not spread even when water droplets fell (the water droplets remained spherical for a long time, as shown below). The treated S claw or glass fiber has excellent hydrophilicity.

In the case of glass fiber, it can be used as a substitute for asbestos.

Claims (1)

[Claims] A compound represented by the following general formula (fflL, R1 is an alkyl group, bird is an alkylene group,
The circle is hydroxymethyl or Al: w is dimethyl, M is bi3Jz4)! A mixed system of 41 species and at least one water-soluble polymer having a hydroxyl group and/or carboxyl group. A method for making glass and glass fiber hydrophilic, which is characterized by the step of: