JPH0663168B2 - Manufacturing method of fiber mat - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a fiber mat used as a reinforcing material for cement products, mainly a glass fiber mat.

(Conventional technology and problems) Conventionally, unsaturated polyester resin powder, saturated polyester resin powder, etc. have been used as binders for glass fiber mats. Mats using these as binders are cement products such as concrete boards. When used as a reinforcing material, it has a major drawback that it inhibits the solidification of cement.

(Means for Solving Problems) As a result of earnest research in view of this point, the present inventors have found that when thermosetting resin powder containing vinyl resin as a main component is used as a binder for a fiber mat, a very stable mat is obtained. They have found that a fiber mat having strength and not inhibiting solidification of cement can be obtained, and completed the present invention.

That is, the present invention is at least one self-curing thermosetting resin selected from the group consisting of alkoxyalkyl group-containing vinyl resin, carboxyl group / hydroxyl group-containing vinyl resin, and carboxyl group / glycidyl group-containing vinyl resin. Vinyl resin; or thermosetting resin containing at least one crosslinking agent-curable thermosetting vinyl resin as a main component, selected from the group consisting of glycidyl group-containing vinyl resin, hydroxyl group-containing vinyl resin and carboxyl group-containing vinyl resin It is an object of the present invention to provide a method for producing a fiber mat, which comprises using the composition powder as a binder.

Here, the thermosetting resin composition containing the above-mentioned various vinyl resins as a main component, which is used in carrying out the present invention, is broadly defined as a specific self-curing thermosetting resin and / or Or a cross-linking agent curing type thermoplastic resin,
If necessary, various known and conventional additives such as a cross-linking agent, a pigment or a leveling agent (such as a flow control agent) may be added,
This refers to a resin composition in a form obtained by dry or wet mixing, and in the usual case, it is used as a so-called powdery substance (powder) in a form prepared by pulverizing to a desired particle size. The vinyl resin used here may be a self-curing one or one that is used in combination with a cross-linking agent, for example, an alkyl ester of (meth) acrylic acid (an alkyl ester having 1 to 18 carbon atoms such as methyl and butyl), styrene. , Vinyltoluene, vinyl acetate, acrylonitrile, fumaric acid dialkyl ester, itaconic acid dialkyl ester and other vinyl monomers having no crosslinkable functional group; methoxymethylacrylamide, butoxymethylacrylamide, (meth) acrylic acid, glycidyl (meth) Suitable vinyl monomers having a functional group such as acrylate, β-methylglycidyl (meth) acrylate, β-hydroxyethyl (meth) acrylate, β-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate are suitable. Selected, after solution polymerization using, for example, a polymerization initiator, which was de-solvent treatment,
Those obtained by suspension-polymerization and then dehydration drying may be mentioned.

Examples of the self-curing thermosetting vinyl resin include those consisting of an alkoxyalkyl group-containing monomer alone, or those combining a carboxyl group-containing monomer and a hydroxyl group-containing monomer, or a combination of a carboxyl group-containing monomer and a glycidyl group-containing monomer. To be

Examples of the vinyl resin having a crosslinkable functional group used in combination with the crosslinking agent include those having a glycidyl group, those having a hydroxyl group, and those having a carboxyl group. As the crosslinking agent used in combination with these, in the case of a vinyl resin having a glycidyl group, for example, adipic acid, sebacic acid, dibasic acid such as decanedicarboxylic acid,
Examples include amine compounds such as dicyandiamide and adipic acid hydrazide. In the case of a vinyl resin having a hydroxyl group,
For example, amino resin such as hexamethoxymethylmelamine,
Blocked isocyanate such as ε-caprolactam adduct of isophorone diisocyanate, trimellitic anhydride,
Examples of the acid include pyromellitic acid, and in the case of a vinyl resin having a carboxyl group, examples thereof include a bisphenol type epoxy resin and triglycidyl isocyanate. Among them, a combination of a vinyl resin having a glycidyl group and a dibasic acid such as decanedicarboxylic acid has the highest mat tensile strength and is preferable.

As the fiber used in the present invention, any known fiber for mat can be used, but glass fiber is mainly used, and carbon fiber and the like are also used.

The thermosetting resin composition mainly composed of the above-mentioned various vinyl resins used in the present invention is usually obtained by mixing desired components, melt-kneading them, and then pulverizing with a suitable pulverizer. It is in a form that is classified so as to have a desired particle size. In this case, the average particle size is usually about 5 to 200 microns (μm) on average.

In the production of a fiber mat, a thermosetting resin composition powder containing a vinyl resin as a main component, which is used as a binder, is usually applied to the fibers by a known method such as an electrostatic spraying method, a spraying method or a spraying method. However, the powder may be applied in a state of being dispersed in water, in which case the particle size is 50 μm.
Finer particle size is preferred. When used as a powder, a metal salt of a higher fatty acid of 2% by weight or less or a fine silica powder can be added as a lubricant in order to improve the fluidity of the powder and prevent the powder from coagulating.

The glass fiber mat can be produced by the method of the present invention by a conventional method. The molten glass base is spun from the bottom of the crucible into a diameter of 9 to 13 μm from a platinum bushing, and 200 to 400 filaments are treated with a sizing agent to form a strand, which is then wound into a cake and dried. It Each strand is used as it is, or 40 to 60 strands are combined and formed into a roving for producing a glass fiber mat. There are two types of glass fiber mats, depending on the manufacturing method. One is the case where chopped strands obtained by cutting strands or rovings into lengths of 25 mm to 50 mm are used, and the product thus obtained is called a chopped strand mat. The other is a continuous mat without cutting the strand, and the product is called a continuous strand mat or school mat.

The chopped strands or continuous strands are placed on a running belt and the binder according to the invention is applied in the next step. The amount of binder to be applied is usually 2.5 to 30% by weight, preferably 3 to 2% with respect to the glass fiber.
It is 0% by weight. If the coating amount of the binder is less than 2.5% by weight, the mat-like shape cannot be maintained, and if it exceeds 30% by weight, the mat tensile strength is sufficiently high, but the mat becomes too hard and the workability deteriorates. Not preferable. Then the belt enters the furnace at about 180-240 ° C for about 1-10
Immediately after leaving for 30 minutes and leaving the furnace, it is compressed by a chill roll and wound into a product. For the evaluation of the products, it is important that the weight is uniform and the distribution of the binder powder is uniform. In the present invention, the products satisfying these conditions were evaluated for the mat tensile strength and the presence or absence of inhibition of cement solidification.

The tensile strength of the glass fiber mat is
The mat was cut into a size having a width of 10 cm and a length of 25 cm, and the mat was stretched in the longitudinal direction and the load when the mat was broken was taken as the tensile strength. An autograph manufactured by Shimadzu Corporation was used as a measuring instrument, and the autograph was pulled at a crosshead speed of 20 cm / min.

For those with or without cement solidification inhibition, cut this glass fiber mat into 30 cm × 30 cm sized pieces, and then put this in a mold of 30 cm × 30 cm × 10 cm.
After pouring water = 25/15 (weight ratio) into the mat, the mat was sufficiently impregnated and left at room temperature for 3 days. Then, the solidification state of the cement was evaluated, and when it was not sufficiently solidified, it was judged that there was inhibition of cement solidification. .

Next, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is by no means limited to these Examples. In the following, "parts" means "parts by weight".

Reference Example 1 (Production of thermosetting resin composition powder) β-methylglycidyl methacrylate 15 parts, glycidyl methacrylate 10 parts, styrene 40 parts, dibutyl fumarate 15 parts, n-butyl methacrylate 20 parts, azobisisobutyronitrile 4 parts and benzoyl peroxide 1
70 parts toluene heated to 100 ° C and n-butanol 3 parts
It was added dropwise to a mixture with 0 parts in 4 hours, and after continuing the reaction for 10 hours, the solvent was removed at 200 ° C. and 1 mmHg until the solvent did not distill, and a solid vinyl having a softening point of 106 ° C. and a molecular weight of 7500. A resin was obtained.

To 100 parts of this vinyl resin, 15 parts of decanedicarboxylic acid and 1 part of Modaflow (a flow control agent manufactured by Monsanto Co.) were added and mixed, and melt-kneaded with an extruder, followed by cooling and crushing,
A thermosetting resin composition powder (binder A) used in the present invention having an average particle size of 120 μm was obtained.

Reference Example 2 (same as above) To a dispersion consisting of 100 parts of water heated to 50 ° C. and 5 parts of calcium phosphate, with stirring, 20 parts of β-methylglycidyl methacrylate, 40 parts of styrene, and 20 parts of dibutyl maleate.
Part, 20 parts isobutyl methacrylate, 4 parts azobisisobutyronitrile, 3 parts lauryl mercaptan,
The temperature was raised to 0 ° C., suspension polymerization was carried out for 10 hours, washing with water and drying to obtain a vinyl resin having a softening point of 105 ° C. and a molecular weight of 7,200.

To 100 parts of this vinyl resin, 15 parts of decanedicarboxylic acid and 1 part of Modaflow were added and mixed, melt-kneaded in an extruder, cooled, pulverized, and thermosetting used in the present invention having an average particle diameter of 70 μm. A resin composition powder (binder B) was obtained.

Reference Example 3 (Same as above) 70 parts of xylene and 30 parts of n-butyl alcohol were added to give 100 parts.
It is heated to ℃, there are 33 parts of methyl acrylate and 30 parts of styrene.
Parts, butyl methacrylate 20 parts, β-hydroxyethyl methacrylate 15 parts, methacrylic acid 2 parts, thioglycolic acid 1 part, azobisisobutyronitrile 3 parts, and quinumehydroperoxide 2 parts are gradually added to the same temperature. The solution obtained by holding for 10 hours was heated to 200 ° C while continuously removing the solvent under reduced pressure (50 to 100 mmHg), and the softening point was 114 ° C.
Of vinyl resin was obtained.

Isophorone diisocyanate 3 is added to 85 parts of this vinyl resin.
Block isocyanate compound obtained by blocking an adduct of 1 mol of trimethylolpropane with methanol
Parts, titanium oxide 50 parts, dibutyltin oxide 1 part, modaflow 1 part, Nikanol LL (Mitsubishi Gas Chemical Co., Ltd. xylene resin) 2 parts were added and mixed with a super mixer,
Melt and knead at 120 ° C for 15 minutes on a heating roll, then cool,
A thermosetting resin composition powder (binder C) used in the present invention having an average particle size of 120 μm was obtained.

Reference Example 4 (Production of Polyester Resin Powder) 743 parts of 2,2-di- (β-hydroxypropoxyphenyl) propane, 232 parts of fumaric acid and 0.39 part of hydroquinone were charged and reacted at 180 to 210 ° C. in a nitrogen stream. , Acid number 15,
A polyester resin having a melting point of 118 ° C. was obtained and crushed to obtain a polyester resin powder (binder D) for comparison and having an average particle diameter of 120 μm.

Examples 1 to 3 and Comparative Example 1 12 parts of the binder shown in Table 1 was applied by electrostatic spraying to 100 parts of glass fiber (chopped strand) cut to a length of 50 mm, and then heated at 200 ° C. for 1 minute. Then, it was compressed with a cooling roll to obtain a chopped strand mat.

Table 1 shows the evaluation results of the tensile strength of this chopped strand mat and the presence or absence of inhibition of cement solidification.

Example 4 N-methylol acrylamide butyl etherification product
15 parts, 30 parts of methyl methacrylate, 40 parts of styrene and 15 parts of dibutyl fumarate, 4 parts of azobisisobutyronitrile and 1 part of benzoyl peroxide were heated to 100 ° C., 70 parts of toluene. Part and 30 parts of n-butanol were added dropwise over 4 hours, and after the completion of the addition, the reaction was continued at the same temperature for 10 hours at 180 ° C. The solvent was distilled off under the condition of 1 mmHg to obtain a solid vinyl resin having a softening point of 110 ° C. and a molecular weight of 7,000.

Then, 3 parts of p-toluene sulfonic acid was mixed in this by a conventional method, and then melted and kneaded by an extruder at 210 ° C. by a conventional method, then cooled and pulverized. Thus, a thermosetting resin composition powder having an average particle diameter of 120 μm was obtained. Hereinafter, this is abbreviated as binder E.

Target chopped strand mats were prepared in the same manner as in Examples 1 to 3 and Comparative Example 1 except that this binder was used.

Thereafter, similarly to Examples 1 to 3 and Comparative Example 1,
When various performances were evaluated, the same results as in Examples 1 to 3 were obtained.

Claims (1)

[Claims] 1. At least one self-curing thermosetting vinyl resin selected from the group consisting of an alkoxyalkyl group-containing vinyl resin, a carboxyl group / hydroxyl group-containing vinyl resin, and a carboxyl group / glycidyl group-containing vinyl resin; Alternatively, a thermosetting resin composition powder containing, as a main component, at least one thermosetting vinyl resin in combination with a crosslinking agent, selected from the group consisting of a glycidyl group-containing vinyl resin, a hydroxyl group-containing vinyl resin and a carboxyl group-containing vinyl resin, A method for producing a fiber mat, which is used as a binder.