JPS6012990B2 - Calcium silicate material and its manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a calcium silicate material reinforced with glass fibers and a method for producing the same.

Conventionally, calcium oxalate materials have been produced by molding a slurry consisting of silicate raw materials, calcareous raw materials, and asbestos fibers, and then subjecting the slurry to high temperature and high pressure treatment under saturated vapor pressure.

However, the demand for reinforcing fibers as an alternative to asbestos has increased in recent years due to the rise in prices due to the depletion of asbestos raw materials and the problem of asbestos contaminating the human body, the so-called asbestos pollution problem. Against this background, alkali-resistant glass fibers were developed and industrially produced, and calcium silicate materials reinforced with the alkali-resistant glass fibers, such as JP-A-48
In Japanese Patent No. 25725, an alkali-resistant glass fiber reinforced calcium silicate material containing Z2 is proposed. However, as a result of experiments conducted by the present inventors, the above-mentioned glass fiber-reinforced calcium silicate material, especially calcium silicate material with a high density of 0.5 to 1.2 ta' blocks used for wall and ceiling materials, has been found to be industrially stable and stable. It has been found that there are various problems in order to produce it at low cost.

That is, the first problem is that when calcium silicate materials are manufactured at low cost using the highly productive sanding method, chopped strand glass fibers cause a sedimentation phenomenon in the slurry, making it difficult to stabilize the homogeneous calcium silicate materials. It turned out that continuous production was not possible. The second problem is that glass fibers using a general sizing agent, i.e., glass fibers using a sizing agent that uses polyvinyl acetate resin as a sizing agent, are difficult to avoid when the sizing agent is used in the steaming process to generate calcium silicate crystals. It was found that the glass fibers were dissolved and the interfacial bonding force between the glass fibers and the matrix was weakened, making it impossible to provide a sufficient reinforcing effect by the glass fibers, which have excellent tensile strength. In view of this situation, the present inventors have completed the present invention as a result of intensive research.The purpose of the present invention is to achieve a structure with a bulk density of 0 with excellent reinforcement efficiency.
．． An object of the present invention is to provide a glass fiber-reinforced calcium silicate material having a strength of 5 to 1.2 days per day, industrially easily and at low cost.

That is, in the present invention, glass fiber filaments are mixed with a sizing agent of 10 to 100% in a matrix made of silicic acid and calcareous material.
Uniformly contains 0.2 to 10% by weight of alkali-resistant chopped glass fiber strands with a disintegration rate of at most 50%, at least 2% by weight of asbestos, and at most 5% by weight of pulp, and has a high density of 0. It is a calcium silicate material characterized by having a heat resistance of .5 to 1.2 m/m.

Furthermore, in the present invention, the silicate raw material and the calcareous raw material are each 30 to 5
% by weight, at least 2% by weight of asbestos, 0.2-10% by weight of alkali-resistant chopped glass fiber strands with a sizing agent attached to glass fiber filaments and 10-100 strands with a defibration rate of at most 50%. This is a method for producing a calcium silicate material, characterized in that a slurry made by uniformly mixing at most 5% by weight of pulp and water is formed into a paper and then subjected to steaming treatment.

The alkali-resistant chopped glass fiber strands with an open strand ratio of 50% or less as shown in the present invention are those having an alkali solubility of at most 4% by weight and a diameter of 5 to 30% to withstand erosion by alkali components during the steaming treatment during the production of calcium silicate materials. It is a chopped strand made of 10 to 100 alkali-resistant glass filaments.

Here, the alkali solubility refers to glass fibers with a fiber diameter of 13±0.2 mm in 100 ml of 95 qo of 10% NaOH aqueous solution.
The figure shows the degree of weight loss of the glass fibers as a percentage when immersed in the water for 1 hour.

The glass suitable for producing the alkali-resistant glass fiber preferably contains at least 7 mol% of Z2, preferably at least 10 mol% or more, more preferably at least 11 mol%, and most preferably at least 11 mol%. It contains .5 mol%.

As a glass composition that satisfies this condition, for example, Si in mol%
02: 50-69%, Z (ko 2: 11.5-13.5%
, R20: 10-22%, K20: 0-7%, RO: 0
~10%, B203:○~5%, AI208:○~5%
(R20 is Na20, up to 3% of which can be replaced with Lj20.

and R' is an alkali metal or an alkali-resistant glass composition such as Zn, Mn, Pb. A glass fiber strand is prepared from the glass composition according to a conventional method.
Glass raw material components are placed in a mullite rubbo or platinum rubbo and heated at a melting temperature of 1300 to 1600°C for 3 to 30 minutes.
The glass is heated for 6 hours to produce a homogeneous glass, which is formed into a rod-like or mercury-like shape.Then, this is led to a melt-spinning process, where 200 to 200 fibers are formed using a melter commonly called a platinum alloy pusher. Hard hole (chip)
1000 ~ while drawing out the molten glass and applying a sizing agent.
It is obtained by winding at a spinning speed of 4000/min.

The diameter of the filament of the alkali-resistant chopped glass fiber strand in the present invention is 5 to 30 m, preferably 9 to 20 m.

If the number is less than 5, the productivity will be low and the cost will be high in industrial production, which is not preferable.

Moreover, if it is more than 30 degrees, the specific surface area of the entire glass fiber becomes small, which is not preferable because the strength of the final product is low. Further, the fiber length of the chopped strand is 6 to 50 ribs, preferably 13 to 25 ribs.

If it is less than 6 ribs, the surface area per chopped strand will be small and the interfacial bonding force with the matrix will be small, so the strength of the final product will be low, which is not preferable.

In addition, if the length exceeds 5, the chopped strands may become entangled with each other or with the floating feathers during the rope-stretching process to homogenize the raw material slurry, resulting in cutting of the chopped strands and, furthermore, the east-gathering property of the chopped strands becomes extremely low. Therefore, the strength of the final product decreases, which is undesirable. The alkali-resistant glass fiber strand from which the chopped strand is obtained is 1
It is composed of 0 to 100 filaments, preferably 30 to 70 filaments.

When the number of filaments is less than 10, spinning operability is poor,
This is undesirable because it causes thread breakage when it is graded, and the rust competitiveness of the glass fibers from the cake is poor, and thread breakage and fluffing occur during disassembly, which is undesirable.

On the other hand, if the number exceeds 100, the surface area per chopped strand obtained will be small, and the interfacial bonding force with the matrix will be small, so the strength of the final product will be low, which is not preferable. The alkali-resistant glass fiber chopped strand according to the present invention has a twill opening ratio of 50% or less, preferably 35% or less, and most preferably 20% or less.

If the open twill rate exceeds 50%, the strength of the final product will decrease, which is undesirable. Here, the open twill rate refers to approximately 1 piece of glass fiber strand with a length of 13 skins, taken out and weighed, and the weight is taken as W and weight. .

The glass fiber strands were treated with 95-100 qo of 1% Na.
OH aqueous solution 1, left for 14 minutes, then lit in a lab mixer for 1 minute, and the glass fibers were thoroughly washed with distilled water to maintain a strand form with 3 or more filaments. Take it out and heat it at 120 pm for 6
The sample was dried for an hour, left to cool in the air, and then weighed. From the weight (W2 weight), the weave ratio was determined using the formula {1}. Kanshin rate (%) =
竿云go This is a numerical value that shows a composite of factors that have a large effect on strength.

That is, if the sizing film has high alkali solubility at high temperatures, the sizing film will melt away during the steaming process that is essential for producing calcium silicate materials.
As a result, the interfacial bonding force with the matrix is reduced and the strength of the final product is reduced. In addition, when the fiber azalea reduces the east-gathering property of the chopped strands, that is, when the strands are defibrated, monofilamentary glass fibers are formed, and the monofilamentary glass fibers have a high density of 0.5 to 1.2 mm/ground. In calcium silicate materials, their tensile strength decreases due to erosion during the combined heat treatment process, resulting in a lower strength of the final product. In order to obtain the open twill rate of the alkali-resistant glass fibers described above, important factors are the composition of the sizing agent that is attached to the glass fiber filaments constituting the strand at the time of grading, and the adjustment of the amount of the sizing agent attached to the glass fibers. The sizing agent used in the present invention preferably contains polyacrylic acid ester resin in an amount of 10 to 8% by weight, preferably 15 to 6% by weight.If the sizing agent is less than 1% by weight, the sizing agent film will easily dissolve during the heat treatment. This is undesirable because the strength of the final product decreases.

On the other hand, if it exceeds 80%, the sizing agent will gum up in the shuto guide or traverse during spinning, resulting in poor yarn quality and is not preferred. The polyacrylic acid ester resin is a homopolymer of acrylic acid ester represented by the general formula 'a} (where R represents an alkyl group having 1 to 18 carbon atoms). or at least 60 mol % of said monomer, preferably 70 mol %, particularly preferably 8 mol % of said monomer;
It refers to a copolymer obtained by polymerizing 0% or more according to a conventional method, such as polyacrylic acid methyl ester resin, polyacrylic acid ethyl ester resin, polyacrylic acid butyl ester resin, polyacrylic acid dodecyl resin, polymethacrylic acid Homopolymers such as methyl ester resin, polymethacrylic acid ethyl ester resin, polymethacrylic acid propyl ester resin, polymethacrylic acid stearyl ester resin, and various polymers thereof, as well as acrylic acid ester monomers represented by the general formula [al] and the following general formula 'b1CHR3=CR4R5 (where R3: day or CH3, R4: day or carbon number 1 to
4 alkyl group, R5: represents day, CI, CN, phenyl group, hydroxyl group, or acetyl group.

) can be used. Polymers obtained by copolymerizing with at least one of various vinyl compounds shown in Examples of the copolymer include ethylene-acrylic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, styrene-methyl methacrylate copolymer, vinyl acetate-butyl methacrylate copolymer, acrylonitrile-methyl methacrylate copolymer. Copolymers etc. can be used. However, since the method of the present invention is characterized by treatment with a sizing agent having alkali resistance, it is usually not preferable to impart a hydrophilic group. is preferred. In addition, in the present invention, polyvinyl acetate, partially saponified polyvinyl acetate, ethylene-vinyl acetate copolymer, and acetic acid are used to improve the gathering properties of the glass fiber strands, as well as to improve spinnability and post-processability. A resin such as a vinyl-acrylic acid ester copolymer or a polyvinyl alcohol epoxy resin may be contained in a proportion of 5% by weight or less.

Also, base oils such as paraffin wax, oxidized polyethylene, vegetable oil, mineral oil, various smoothing softeners such as cationic surfactants, nonionic surfactants, anionic surfactants, and various cups such as pinylsilane, aminosilane, epoxysilane, etc. The ring agent is contained in a proportion of not more than 3% by weight. Furthermore, plasticizers such as dimethyl phthalate and dibutyl phthalate, and some sugars such as glucose, sucrose, mannose, dextrin, starch, etc. may be appropriately added and mixed into the sizing agent.

The adhesion amount of these sizing agents to glass fiber is 0.5~
4% by weight, preferably 1-3% by weight.

If the adhesion amount is less than 0.5% by weight, yarn breakage occurs during the yarn-proofing of gas fibers, resulting in poor spinning operability. Furthermore, the fibrillation rate of the obtained chopped strands increases, which undesirably lowers the strength of the final product. On the other hand, if it exceeds 4% by weight, the resulting glass fiber strands have poor unravelability from the cake, become fluffy, and even break off of the strands, which is undesirable. The calcium silicate material according to the present invention is
The slurry consists of a matrix raw material consisting of an acidic raw material and a calcareous raw material, alkali-resistant chopped glass fiber strands, asbestos fibers and pulp, and each of these raw materials is uniformly mixed in water using a paper making machine. It is produced by steaming the raised material.

The added amount of the alkali-resistant chopped glass fiber strands according to the invention is 0.2-1% by weight.

0. If the amount is less than 1% by weight, the reinforcing effect of the glass fibers cannot be sufficiently exerted, and the strength of the final product is therefore undesirable.

On the other hand, if it exceeds 1% by weight, it is not possible to obtain a homogeneous slurry due to the entanglement of the glass fibers, and therefore it is not possible to obtain a final product with stable physical properties, which is not preferable. In the present invention, asbestos is added in an amount of at least 2% by weight, preferably at least 5% by weight.

If it is less than 2% by weight, paper forming properties will be poor.

That is, the solid content of the raw material slurry cannot be stably and homogeneously extracted using a paper making machine, which is not preferable. Further, in order to improve the above-mentioned paper forming properties, pulp is added in an amount of at most 5% by weight. If it exceeds 5% by weight, the resulting final product will have poor fire and heat resistance, which is undesirable.Furthermore, in order to develop the color when drying the product at a high temperature, an inefficient drying method that requires a long time at a low temperature will have to be adopted. I don't get it and it's not good.

In the present invention, asbestos improves paper forming properties as described above, and also has the effect of increasing the strength of the final product due to its effect as a reinforcing fiber.

Glass soso mainly has the effect of increasing the strength of the final product,
Pulp has the effect of improving paper forming properties. Therefore, in order to maintain good paper forming properties and high strength of the final product, the ratio of the amount of glass woven material, asbestos and pulp added is an extremely important factor. Assuming that the amount of fiber added is G weight %, the amount of asbestos added is A weight %, and the amount of pulp added is P weight %, the following range is desirable. '1} Added amount of asbestos is 5% by weight
In the following case 3t09-0.17ASGSI2.25-0
．． 75A3・67 mountains.

・33AmiP■ When the amount of asbestos added is 15% by weight or less 3.38-0, 23A≦G≦10.25-0.3 Pine 3.
010.2ASPS9.1310. Father Duke '3' If the amount of asbestos added is 25% by weight or less, GS9. Total 0.33AP
≦6.88-0.23A '4) If the amount of asbestos added exceeds 25% by weight, GSI. 7
5PSI. 25 In the present invention, the siliceous raw material and the lime resource material are each selected within a range of 30 to 5% by weight.

At that time, the matrix is evaporated to make Ca○
The molar ratio of the lotus acid raw material and the calcareous raw material is 0 from the viewpoint of industrial productivity, since it produces zo/trite crystals with an equimolar ratio of /Si02 or tobermorite crystals with a Ca○/Si02 ratio of approximately 0.8. It is in the range of .8 to 1.2. The siliceous raw materials mentioned above include siliceous wood, silica sand, silica, siliceous acid white, ferrosilicon dust, silicon dust, etc., and the calcareous raw materials include, for example, quicklime, slaked lime, carbide mulberry, etc.

Also, cement, clays such as bentonite, sodium silicate,
Calcium chloride, gypsum, etc. may be added in a proportion of 2% by weight or less.

In the present invention, a raw material slurry may be heat-treated at 60 to 100°C to produce calcium oxalate gel, and then paper-formed.

The present invention improves bending strength, tensile strength and impact strength,
In addition, a calcium silicate material having a bulk density of 0.5 to 1.2 m/s can be produced industrially easily and at low cost.

The present invention will be explained below with reference to Examples.

Example 1 Si02: 66.5%, Si02: 12%, Li
20:2%, Na20:155%, K20:3%, B2
Glass having a composition of 0.03: 0.5% and N203: 0.5% (alkali solubility 1.3%) was heated using a platinum Lupo.
It was melted at 450°C for 10 hours and molded into a marple shape with 15 ribs.

Next, chips with an inner diameter of 1.5 mm were extruded into fibers using a platinum-rhodium (80/20%) alloy bushing with an internal volume of 1, and the number of fibers was varied at 1280 qo. Fiber mug 1 at a winding speed of /min
Glass fibers having different numbers of filaments per strand were prepared by winding 3 mm of glass fibers. Polyacrylic acid ester resin (3-514: manufactured by Kanebo NSC) 5
weight% of polyvinyl acetate resin (VQ-553: Bell grade N
10% by weight of a cationic surfactant (Cation Softener
An aqueous emulsion solution containing 5% by weight of a mold component consisting of 5% by weight and 5% by weight of dibutyl phthalate was used as a sizing agent and was applied to the glass fibers using a roller type oiling device. Calcium hydroxide 42% by weight,
Diatomite 35% by weight, silica sand 7% by weight, cut length 25 ribs, glass fiber 4% by weight, asbestos 1% by weight and pulp 2% by weight
Using a slurry having a solid content of 1,000 ml, the slurry was molded to a thickness of 6 willows and steamed at 180 qo for 14 hours under saturated steam pressure.

The bending strength and impact strength of the obtained calcium silicate plate dried at 110 qo for 24 hours were measured (however, the measurement was performed on the product 1 hour after the start of paper forming).
). Furthermore, the stability of the glass fiber-containing slurry was evaluated by the following method.

The paper making machine was operated continuously for 24 hours, and the bending strength of the molded calcium silicate plate was measured after 1 hour and 2 hours.
〇, and respectively. 24.

〇24/0. <0.93 ×, 0.93S024
/○, those with <0.97 are △, 0.97S. 24/0,
Those were marked as ○.

The results are shown in Table 1.

Table 1 From Table 1, the number of filaments in the strand is 10.
-100, preferably 30 to 70, a glass fiber reinforced calcium silicate material with good slurry stability and high bending strength can be obtained.

If there are less than 10 fibers, the glass fiber cake becomes fluffy during the debroiling process, contains a large amount of monofilament glass fibers, and has a high open twill ratio, resulting in low bending strength.

On the other hand, if the number exceeds 100, the stability of the slurry decreases due to sedimentation of the glass fiber strands. Example 2 According to Example 1, chopped strands were prepared in which the number of filaments in the strand was 50, the number of glass fibers was 13 mm, and the cut length of the strand was 13 and the amount of sizing agent attached was different.

Polyacrylic acid ester resin (32A-514: Kanebo N
25% by weight of ethylene-vinyl acetate copolymer (M-1000: manufactured by Kanebo NSC), 1% by weight of epoxy resin (EA-1: manufactured by Kanebo NSC) and its curing agent. 5% by weight, 5% by weight of cationic surfactant (Cation Softener x: manufactured by Onyx Co., Ltd.), 5% by weight of polyethylene glycol (molecular weight 2000), and 1% by weight of epoxysilane coupling agent (AI87: manufactured by Nippon Junika Co., Ltd.) An aqueous emulsion solution containing 25% by weight of solids was used as a sizing agent, and the amount of adhesion of the sizing agent to the glass fibers was varied by changing the rotational speed of a drop-on type oiling bag. 4% by weight of calcium hydroxide, 40% by weight of desert earth, 3% by weight of glass fiber.
A slurry having a field type content of 5% by weight, 1% by weight of asbestos, and 0.5% by weight of pulp was gelled for 2 hours at 9 pcs of water, and then made into a sheet with a thickness of 12 willows. The material was steam-treated at 180o0 for 12 hours, and the properties of the obtained calcium silicate plate were measured.

Note that the method of drying the measurement sample and the sampling method were the same as in Example 1.

The results are shown in Table 2.

Table 2 From Table 2, when the opening ratio is 50% or less, preferably 35% or less, most preferably 20% or less, a low bulk density glass fiber reinforced calcium silicate material with excellent bending strength and impact strength can be obtained. be able to.

Example Si02:67%, Zr02:12 at 3 mol%
%, Li20: 2%, Na20: 16%, K20: 3%
A glass having the following composition (alkali solubility u%) was melted in a platinum rubbo at 1500 oo for 1 hour, and 8 side x 2
It was molded into a rod shape with 5 supports.

Then, using a pusher made of a platinum-rhodium (80/20%) alloy with an internal volume of 2 and having 400 chips with an inner diameter of 2 ribs, it was extruded into a fiber shape and wound up. The sizing agent was also applied to the glass fibers using a roller type oiling device. By changing the winding speed of the glass fiber, the amount of glass rod supplied to the bushing, the temperature of the bushing, and the rotation speed of the oiling device, the number of filaments in the strands with different fiber diameters and amounts of sizing agent deposited was 50. I made some glass fiber. Here, 35% by weight of polyacrylic acid ester resin (32A-514: manufactured by Kanebo NSC), 20% by weight of polyacrylic acid ester resin (Bentite M: manufactured by Kanebo NSC), polyvinyl acetate resin (V42)
50: Kanebo NSC Co., Ltd.) 25% by weight, cationic surfactant (Cortamine P86: Kao Atlas Co., Ltd.) 8% by weight
, paraffin smoothing agent (Word Processing Set GF: Takemoto Yushi Co., Ltd.) 2% by weight, aminosilaso coupling agent (AI
An aqueous emulsion solution containing 25% by weight of solids consisting of 5% by weight of lOO (manufactured by Nippon Kunica Co., Ltd.) and 5% by weight of dibutyl phthalate was used as the sizing agent. Using glass fibers with various fiber diameters and sizing agent adhesion amounts, the third
Using the raw material slurry with the blending composition and heat treatment shown in the table, it was molded into a paper having a thickness of 6 sides and was steam-treated at 180°C for 16 hours, and the properties of the obtained calcium oxalate plate were measured.

The method of drying the measurement sample and the sampling method were the same as in Example 1. The paper forming plasticity was evaluated by the following method.

The solid content of the raw material slurry passes through the cylinder of the paper making machine,
× indicates that paper making and molding is difficult; △ indicates that solid matter can pass through but paper making is possible; and paper making and forming can be performed successfully with almost no solid matter passing through. It was marked as ○.
Further, the homogeneity of the raw material slurry was evaluated by the following method.

A case where the glass fibers were entangled with each other in the slurry and caused a boring phenomenon was evaluated as ×, a case where the glass fibers were mixed unevenly due to intertwining with each other was evaluated as Δ, and a case where the glass fibers were uniformly mixed was evaluated as ○. The heat resistance of the obtained strong acid calcium plate was determined according to JIS-A5418 by heat-treating it at 650 o'clock for 3 hours, measuring the rate of change in length before and after the treatment, and if the rate of change exceeded 2%, Those within % were marked as ○.

The results are shown in Table 3.

As is clear from Table 3, the glass fiber filaments are concentrated in the range of 10 to 100 with a sizing agent, and the alkali-resistant glass fiber chopped strands with a scale fiber ratio of at most 50% are mixed with 0.2 to 1. % by weight, containing at least 2% by weight of asbestos and at most 5% by weight of pulp, and is subjected to paper forming and steam V heat treatment to achieve a high density of 0.5 to 1.2 mm/min.
It is important that a calcium silicate plate, which is a base material, is obtained, and that the raw material slurry during production has excellent homogeneity, paper moldability, and material properties.

Claims (1)

[Scope of Claims] 1. Alkali-resistant chopped strands of glass fibers made of silicic acid and calcareous materials, in which 10 to 100 glass fiber filaments are bundled with a sizing agent in a matrix and have a defibration rate of at most 50%. Calcium silicate material, characterized in that it uniformly contains 2 to 10% by weight of asbestos, at least 2% by weight of asbestos and at most 5% by weight of pulp, and has a high density of 0.5 to 1.2 g/cm^3. 2. The calcium silicate material according to claim 1, wherein the glass fiber has an alkali solubility of 4% by weight or less. 3. Calcium silicate material according to claim 1, wherein the glass fibers contain at least 10 mol% ZrO_2. 4 Glass fiber chopped strands have a diameter of 5 to 30μ
The calcium silicate material according to claim 1, wherein 30 to 70 filaments are collected. 5 Defibration rate of chopped glass fiber strand is 35%
The calcium silicate material according to claim 1, which is as follows. 6 Defibration rate of chopped glass fiber strand is 20%
The calcium silicate material according to claim 1, which is as follows. 7 Glass fiber chopped strand length 6-50m
The calcium silicate material according to claim 1, which is m. 8 30 to 50% by weight of each of silicic raw materials and calcareous raw materials
, at least 2% by weight of asbestos, and 0.2 to 10% by weight of chopped strands of alkali-resistant glass fibers, which are made by adhering a sizing agent to glass fiber filaments and bundle 10 to 100 strands with a defibration rate of at most 50%. A method for producing a calcium silicate material, which comprises forming a slurry made by uniformly mixing at most 5% by weight of pulp and water, and then subjecting it to steam treatment. 9. The method for producing a calcium silicate material according to claim 8, wherein the sizing agent contains 10 to 80% by weight of polyacrylic acid ester resin in solid content. 10. The method for producing a calcium silicate material according to claim 8, wherein the sizing agent contains 15 to 60% by weight of polyacrylic ester resin in solid content. 11. The method for producing a calcium silicate material according to claim 8, wherein the amount of the sizing agent deposited is 0.5 to 4% by weight. 12. The method for producing a calcium silicate material according to claim 8, wherein the amount of the sizing agent deposited is 1 to 3% by weight.