JPH021101B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a treatment agent for glass fibers. For more details, see the following general formulas (), (), (), (),
0.01 mol% of at least one copolymer unit selected from the copolymer units shown in () or ()
The present invention relates to a glass fiber treatment agent containing cationic group-modified polyvinyl alcohol containing ~20 mol%. (Here, A means a group that connects the nitrogen atom in B and the nitrogen atom of the amide group, and B is

[Formula] Also teeth

[Formula], D means an aliphatic group connecting the nitrogen atom and oxygen atom in B,
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ¹¹ and R ¹² each mean a hydrogen atom or a lower alkyl group, and R ⁶ and R ¹⁰ each mean a lower alkyl group which may contain a substituent. (R ⁷ , R ⁸ and R ⁹ each mean a hydrogen atom, a lower alkyl group or a phenyl group, R ¹³ means a lower alkyl group, and X ^- means an anion) Glass fiber is a reinforced plastic material. Glass fibers, especially alkali-resistant glass fibers, are widely used as reinforcing materials, and in recent years, glass fibers, particularly alkali-resistant glass fibers, have been attracting attention as reinforcing materials for reinforced cement products. Glass fibers are usually treated with a focusing agent immediately after their formation. This treatment is carried out for the purpose of effectively acting as a protective lubricant against various types of friction that the glass fibers are subjected to during the manufacturing process. Therefore, as such a treatment agent, a film-forming material is usually used that forms a protective film on the surface of the fibers and also adhesively encapsulates the fibers to protect the fibers from breaking and fuzzing due to friction. It will be done. Conventionally, many materials have been proposed as the film-forming agent, such as starch, modified starch, dextrin, amylose, carboxymethyl cellulose, and water-soluble polymer materials such as ordinary unmodified polyvinyl alcohol (hereinafter simply abbreviated as PVA). There is. Among these, starch has been widely used for reasons such as economic efficiency, but starch-based focusing agent compositions suffer from spoilage due to the aging properties of starch, have poor stability over time, and This method has drawbacks such as the so-called migration phenomenon in which the solid content of the treatment composition moves to the outer surface of the winding yarn or bobbin made of bundled glass fibers. Chemically modified starches, dextrins, amyloses, etc. have similar drawbacks. In the case of normal PVA, there is no change over time due to rotting etc. as with starch-based products, but there are also problems with changes in viscosity over time (thickening) and problems with so-called migration phenomena. The present inventors investigated glass fiber treatment agents that do not have such drawbacks, and found that the general formulas (), (),
Cationic group modification containing 0.01 mol% to 20 mol% of at least one type of copolymerized unit selected from the copolymerized units represented by (), (), (), or ()
In addition to discovering that PVA is superior, we have also established an industrially advantageous method for introducing cationic groups into PVA, leading to the present invention. Conventionally modified PVA containing cationic groups in the molecule (hereinafter simply referred to as cationically modified PVA)
Sometimes abbreviated as PVA. ) as a film-forming agent as a treatment agent for glass fibers is completely unknown. Although several methods for introducing cationic groups into PVA have been proposed, all of them have drawbacks in their modification methods, making it difficult to produce them industrially. It is presumed that this is because it could not be considered to be used as a treatment agent for glass fibers. The major features of the glass fiber treatment agent of the present invention, which uses a specific cationic group-modified PVA, are that it has excellent adhesion to glass fibers and has good focusing properties, and is also characterized by the absence of so-called migration phenomena. . The reason why the migration phenomenon of the present invention is not observed is that of ordinary unmodified PVA and anion-modified PVA containing anionic groups.
The specific cation-modified PVA of the present invention is significantly superior to PVA, and the reason is not clear.
This is thought to be due to the fact that the treatment agent has excellent adsorption properties to negative glass fibers due to its cationic group, which makes the adhesion of the treatment agent to the glass fibers good and more uniform. It is thought that this is due to the same reason. Furthermore, glass fibers treated with the treatment agent of the present invention can be used as reinforcing materials for reinforced cement products. It shows better bending strength and impact strength than when using In particular, when the reinforced cement products are treated at high temperatures, the reinforcing glass fibers tend to deteriorate due to the alkali of the cement, so the performance of the cement products is considerably reduced in the case of ordinary unmodified PVA or anion-modified PVA.
It was found that the glass fiber treatment agent containing the cation-modified PVA of the present invention exhibits excellent characteristics with little deterioration in performance. As described above, the treatment agent of the present invention is particularly excellent as a glass fiber treatment agent for reinforced cement products. It also has better water solubility and viscosity stability than ordinary PVA. Of course, since it is a synthetic product, it does not have the disadvantage of changing over time due to spoilage, which is the case with starch-based products. Although the glass fiber treatment agent of the present invention essentially uses a specific cationic group-modified PVA as a film forming agent, other conventional film forming agents may also be used in combination. Furthermore, emulsifiers, dispersants,
Various optional additives such as binders, plasticizers, lubricants, surfactants, preservatives, etc. can be added as necessary. The present invention will be explained in more detail below. Cationic group modification used in the present invention
The cationic group contained in the molecule of PVA refers to the primary amine, secondary amine or tertiary amine contained in the copolymerized unit represented by the general formula (), () or (); the general formula (), () or Quaternary ammonium salt contained in the copolymerized unit shown in ();
At least one cationic group selected from imidazole contained in the copolymerized unit represented by the general formula (); and imidazolinium contained in the copolymerized unit represented by the general formula (), and these cationic groups are It is a chemical structural unit that dissociates inside and becomes positively charged. Modified PVA containing copolymerized units represented by the general formulas (), (), (), or () not only exhibits cationic activity, but also can be used industrially to introduce cationic groups and obtain a degree of saponification according to the purpose. Both methods are preferred because they are stable and easy to implement. The production of modified PVA containing copolymerized units represented by the above general formulas () to () is carried out using vinyl esters, especially vinyl acetate, and the following formulas (a) to (d). (Here, R ¹ to R ³ , R ⁷ to R ¹⁰ , X ^- , A, B, D
The meaning of is the same as above. ) in the presence of a radical polymerization initiator, and then an alkali or acid catalyst is applied to the alcohol solution of the copolymer to form vinyl ester units in the copolymer. It can be effectively and easily produced by partially or highly saponifying it to form vinyl alcohol units depending on the purpose. In the monomer represented by general formula (a), R ¹ and R ² are hydrogen atoms or lower alkyl groups, but hydrogen atoms or methyl groups are usually preferred, and furthermore, they have a high polymerization rate in the copolymerization reaction with vinyl acetate. In this respect, a hydrogen atom is preferable. R ³ is also a hydrogen atom or a lower alkyl group, but usually a hydrogen atom or a methyl group is preferred. B is an amino group

[Formula] or quaternary ammonium salt

[Formula], R ⁴ and R ⁵ represent a hydrogen atom or a lower alkyl group, R ⁶ represents a lower alkyl group which may contain a substituent, and X ⁻ represents an anion.
R ⁴ , R ⁵ , and R ⁶ are preferably all methyl groups for normal purposes, but for special purposes, they may be lower alkyl groups such as ethyl or propyl groups, or methylol groups or cationic groups for the purpose of imparting reactivity. Lower alkyl groups containing substituents such as aminoalkyl groups are also used for the purpose of improving density. As X, a halogen atom such as chlorine, silium, or iodine, or CH ₃ OSO ₃ or CH ₃ C ₆ H ₄ SO ₃ is preferable, and a chlorine atom is particularly preferable from the viewpoint of economy, safety, or physical properties of modified PVA. When B is in the form of a quaternary ammonium salt, the effects of the present invention can be exhibited even with primary to tertiary amines, which are preferable for ease of handling in the production of modified PVA. Amino group B
As the group A that connects the nitrogen atom in the amide group with the nitrogen atom of the amide group, any group containing a stable bond can be used, but a linear or branched aliphatic group is usually used. Among the monomers represented by the above general formula (A), the following are specific examples of monomers in the form of tertiary amines. N-(2-dimethylaminoethyl)acrylamide, N-(2-dimethylaminoethyl)methacrylamide, N-(3-dimethylaminopropyl)acrylamide, N-(3-diethylaminopropyl)acrylamide, N-(3-dimethyl aminopropyl) methacrylamide, N-(3-
diethylaminopropyl) methacrylamide, N
-(1,1-dimethyl-3-dimethylaminopropyl)acrylamide, N-(1,1-dimethyl-3-dimethylaminopropyl)methacrylamide, N-(1,1-diethyl-3-dimethylaminobutyl)acrylamide , N-(1-methyl-
1,3-diphenyl-3-diethylaminopropyl)methacrylamide, N-(3-dimethylaminohexyl)acrylamide, N-(3-methylethylaminopropyl)methacrylamide, N-
Methyl-N-(3-dimethylaminopropyl)acrylamide, N-(2,2-dimethyl-3-dimethylaminopropyl)acrylamide, N-
(2,2-dimethyl-3-dimethylaminopropyl)methacrylamide, N-(2,2-dimethyl-3-dimethylaminopropyl)crotonic acid amide, N-(3,3-dimethyl-4-dimethylaminobutyl) Acrylamide, N-(3,3-dimethyl-4-dimethylaminobutyl)methacrylamide, N-(3,3-dimethyl-4-dimethylaminobutyl)crotonic acid amide. Among the monomers represented by the above general formula (a), those in the form of quaternary ammonium can be easily obtained by quaternizing the above-mentioned tertiary amine type monomer with a commonly used quaternizing agent. Can be done. The following four types of monomers among the various examples mentioned above as monomers represented by the above general formula (A), namely, N-(1,1-dimethyl-3-dimethylaminopropyl)acrylamide trimethyl-(3-acrylamide-3,3-
dimethylpropyl) ammonium chloride N-(3-dimethylaminopropyl)methacrylamide Trimethyl-(3-methacrylamidopropyl) ammonium chloride In producing the modified PVA of the present invention, the polymerization rate,
It is excellent in terms of stability of the amide group and economic efficiency during monomer production. Furthermore, examples of the monomer shown in (b) above include the following. 1-vinylimidazole, 1-vinyl-2-methylimidazole, 1-
Vinyl-2-ethylimidazole, 1-vinyl-
2-phenylimidazole, 1-vinyl-2,
4,5-trimethylimidazole. Further, the monomer represented by the above general formula (c) can be easily obtained by quaternizing the monomer represented by the above general formula (b) with a commonly used quaternizing agent. Examples of the monomer represented by the above general formula (2) include dimethylaminoethyl vinyl ether, dimethylaminopropyl vinyl ether, quaternized products thereof, and vinyloxyethylamine. In addition, the cationic group-modified PVA has the general formula ()
or Modifications containing copolymerized units shown in parentheses
PVA is also useful in the present invention. Up until now, it has been more difficult than expected to incorporate vinylamine copolymerized units into PVA, and no industrially effective method has been known yet. Copolymerizing an amide, especially N-vinylacetamide, N-vinyl-N-methylacetamide, or N-vinyl-N-methylformamide in the presence of a radical polymerization initiator, and then hydrolyzing the copolymer. Accordingly, N
- It has also been found that all of the amide groups in the vinylalkylamide units can be hydrolyzed to vinylamine units, thus making it possible to produce modified PVA containing any amount of vinylamine units. In addition, the modified product obtained by decomposing the amide group in this way
The above () is obtained by applying a quaternizing agent to an aqueous solution of PVA.
It can also be in the form of a quaternary ammonium salt as shown in the formula. Conventionally reported methods for producing cation-modified PVA include copolymerizing vinyl pyridine and vinyl acetate, followed by saponification, and copolymerizing N-vinylphthalimide or N-vinyl succinimide with vinyl acetate, followed by saponification, followed by alkali or Method of decomposing imide group with hydrazine, method of aminoacetalization or aminobenzacetalization of PVA under acid catalyst, alkoxydimethylamine, glycidyltrimethylammonium hydrochloride or 3-chloro-2-hydroxypropyltrimethylammonium in PVA A method of reacting a hydrochloride, a method of adding acrylamide to PVA and then introducing an amino group by Hofmann decomposition are known. These cationic modifications
The cationization process itself is difficult to implement industrially in the production of PVA. Cationic group modification used in the present invention
General formula (), (), (), (), ( in PVA
)
The content of at least one copolymerized unit selected from the copolymerized units represented by or () is 0.01 mol% or more as the lower limit is 0.01 mol% or more since the effect is exhibited even with a relatively small content, and the upper limit is 20 mol%.
The following are required. A more preferable range is 0.1 to 15
It is mole%. If the degree of modification exceeds 20 mol %, it is not preferred as a film-forming agent because it is highly hygroscopic and becomes sticky, causing the treated glass fiber strands to become sticky and difficult to handle. The degree of saponification is usually preferably in the range of 70 to 100 mol%. Further, the degree of polymerization is usually selected from the range of 300 to 3000. The viscosity of a 4% aqueous solution at 20℃ is used as a guideline for the degree of polymerization.
A range of 3.0 to 150 centipoise (cps) is desirable. As the lubricant, those used for ordinary fiber processing can be used. For example, nonionic lubricants such as animal oils, vegetable oils, hydrogenated derivatives thereof, glycols, esters of glycols, and cationic lubricants such as amine condensates of fatty acids are preferred. Since cation-modified PVA itself has an emulsifying effect, it is not necessary to use an emulsifier, but a conventional emulsifier can be used if necessary. For example, polyethylene glycol ester, polyoxyethylene alkyl ether, sorbitan fatty acid ester polyoxyethylene alkylamine, polyalkylene amine, etc. can be used. Moreover, a plasticizer can be used as necessary. For example, polyhydric alcohols such as ethylene glycol and glycerin, ethyleneimine formamide, ethanolamine, etc. can be used. Other film-forming agents include starch, dextrin, modified starch, ordinary unmodified PVA, gelatin, casein, etc., cationically modified as necessary.
May be used in combination with PVA. These materials can be preferably used, for example, in the following blending ratios, and are attached to glass fibers by a conventional method. Cation modified PVA 1.0-10 (parts by weight) Lubricant 0-8 Emulsifier 0-2 Water 100 Next, the present invention will be specifically explained with reference to Examples and Control Examples, but the present invention is limited to these Examples. It's not a thing. Example 1 Contains 2 mol% of 1-vinyl-2,3-dimethylimidazolinium chloride as a copolymerized unit,
A cationic group-modified PVA having a saponification degree of 98.5 mol% and a 4% aqueous solution having a viscosity of 28 cps at 20° C. was dissolved in water by heating to prepare an aqueous solution of the modified PVA. This aqueous solution was applied to glass fibers using the conventional dipping method described below, and adhesion was measured to evaluate the cohesiveness of the glass fibers. That is, the modified plain weave cloth (18 pieces/25 mm x 20 pieces/25 mm)
It was immersed in a PVA aqueous solution and dried at 105℃ for 15 minutes, then cut into 25mm x 15cm pieces.The warp threads were cut alternately at 2.5cm from the end so that the length of the warp threads was 10cm.This was used as a sample. do. Both ends of the sample were held using an Instron tensile tester and pulled at a speed of 10 cm/min to measure adhesion, and at the same time the amount of polymer attached to the glass fiber was measured. I asked for strength. The results are shown in Table 1. As a control example 1, the same conditions as in Example 1 were used except that ordinary unmodified PVA with a saponification degree of 98.0 mol% and a 4% aqueous solution having a viscosity of 28.5 cps at 20°C was used instead of the modified PVA of Example 1. The glass fibers were treated and the adhesive strength was measured. The results are shown in Table 1. As a control example 2, instead of the modified PVA of Example 1, an anionic group-modified PVA containing 2 mol% of crotonic acid as a copolymerized unit, a saponification degree of 98.3 mol%, and a 4% aqueous solution having a viscosity of 27 cps at 20°C was used. Glass fibers were treated under the same conditions as in Example 1 except for the use, and the adhesive strength was measured. The results are shown in Table 1. As is clear from Table 1, the cationic group-modified PVA obtained in Example 1 was found to have better adhesive properties and fiber cohesiveness than the comparative example. Furthermore, strands made of glass fiber monofilaments bundled using this PVA aqueous solution and threads made by twisting them together had lower fluff than the control example, and exhibited uniform strength characteristics with fewer scraps.

[Table] Example 2 Trimethyl-(3-acrylamide-3,3-
A copolymer of dimethylpropyl) ammonium chloride and vinyl acetate is saponified to form trimethyl-
(3-Acrylamido-3,3-dimethylpropyl) A cationic group-modified PVA containing 2.5 mol% of ammonium chloride units, a degree of saponification of vinyl acetate units of 99 mol%, and a 4% aqueous solution having a viscosity of 29 cps at 20°C was added to water. A size composition having the following blending ratio was prepared by heating and dissolving. Cationic modified PVA 4.0 parts by weight Hydrogenated vegetable oil 2.0 parts by weight Tetraethylenepentamine distearate
0.2 parts by weight Water 100 parts by weight The above composition solution was applied to an alkali-resistant glass fiber filament that had just been continuously spun using a conventional dipping method, bundled, and wound onto a shaping tube. Furthermore, the winding bobbin was treated at 120° C. for 20 minutes and dried.
The obtained strands of the treated fibers and yarns made by twisting them all had low fuzz, had few scraps, and exhibited uniform strength characteristics. Select thread samples from both the inner and outer parts of the obtained thread,
This was heated to 400° C. in a furnace, and the weight loss was measured as a percentage of the weight of the coated strand before heat cleaning. The results are shown in Table 2. As a control example, the same procedure as in the above example was performed except that unmodified PVA (degree of saponification 97.5 mol%, viscosity of 4% aqueous solution 29.5 cps) was used. 2.5 acrylic acid copolymerized units obtained by copolymerizing and saponifying vinyl acetate.
A control example is an example in which the procedure was carried out in the same manner as in the above example except for using anionic group-modified PVA containing mol%, saponification degree of vinyl acetate units of 98 mol%, and viscosity of 4% aqueous solution of 27 cps. Table 2 shows the results as 4.
It was shown to.

[Table] It can be seen that the treatment composition of the present invention shows slight fluctuations inside and outside the wound yarn, while the strands treated with unmodified PVA and anion group-modified PVA show large fluctuations. This shows that the glass fiber treatment composition made of cation-modified PVA of the present invention has excellent performance in that it adheres more uniformly and has no tendency to migrate. The treated glass fiber strands thus obtained were used to make reinforced cement products and their performance was evaluated. That is, 100 parts by weight of Bortland cement, 85 parts by weight of river sand (particle size of 1 mm or less), and 45 parts by weight of water are uniformly mixed in a mixer to form a slurry. Spray this slurry onto the wooden formwork with a spray gun and at the same time cut the above strands to 25mm using a cutter.
Cut into long pieces and mix uniformly into the cement slurry. However, the amount of fiber mixed in is 9% by weight based on cement.
It is. After being left for one day, it was removed from the mold and cured in water at 20°C for 4 weeks. Glass fiber reinforced cement product sample obtained here (thickness 10mm, size 40mm x 100mm)
Impact strength (using Sialby impact tester Kg・cm/
cm ² ) and bending strength (Kg/cm ² using Instron) were measured and shown in Table 3 before treatment. The impact strength and bending strength of this sample after being left in water at 60°C for one week were measured and are shown in Table 3 after treatment.

[Table] Table 3 shows that glass fibers excellent as reinforcing materials for cement products can be obtained by treatment with the cation-modified PVA of the present invention, and that the deterioration in performance is particularly small when heat treated. This decrease in performance due to heat treatment is thought to be due to the alkalinity of cement corroding the glass fibers and reducing their performance, and this suggests that the cation-modified PVA of the present invention is effective in preventing this deterioration of the performance of glass fibers. It will be done. Examples 3 to 8 In place of the cationic group-modified PVA of Example 2,
Glass fibers were bundled in the same manner as in Example 2, except that the cationic group-modified PVA shown in Example 4 was used. A fiber-reinforced cement product was made using the treated fibers in the same manner as in Example 2, and its performance was evaluated. The results are shown in Table-5.

【table】

【table】

[Table] As can be seen from Table 5, the cement-reinforcing glass fibers treated with the cationic group-modified PVA of the present invention exhibit excellent performance.

Claims (1)

[Claims] 1 The following general formulas (), (), (), (), (
)
A treatment agent for glass fibers containing cationic group-modified polyvinyl alcohol containing 0.01 mol% to 20 mol% of at least one copolymerized unit selected from the copolymerized units represented by (). (Here, A means a group that connects the nitrogen atom in B and the nitrogen atom of the amide group, B means [formula] or [formula], and D connects the nitrogen atom and oxygen atom in B. means an aliphatic group that
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ¹¹ and R ¹² each mean a hydrogen atom or a lower alkyl group, and R ⁶ and R ¹⁰ each mean a lower alkyl group which may contain a substituent. (wherein, R ⁷ , R ⁸ and R ⁹ each represent a hydrogen atom, a lower alkyl group or a phenyl group, R ¹³ represents a lower alkyl group, and X ⁻ represents an anion).