JPS6134290A - Polyvinyl vinyl chloride resin tile - Google Patents

Abstract

PURPOSE:The titled tile having strength without using asbestos, and improved processing properties, comprising <= a specific amount of vinyl chloride resin and a specified amount of ground calcium carbonate subjected to surface treatment. CONSTITUTION:22wt% (in resin tile) vinyl chloride resin is blended with 2- 20wt% ground calcium carbonate which is subjected to surface treatment by treating ground calcium carbonate with a modified resin acid, fatty acid, its ester, petroleum resin, coumarone resin, etc. by Henschel mixer, kneaded at 100-150 deg.C, and processed into a polyvinyl chloride resin tile.

Description

Detailed Description of the Invention "Field of Industrial Application" The present invention relates to the improvement of polyvinyl chloride resin tiles, and more specifically, to the improvement of polyvinyl chloride resin tiles, which have sufficient strength even when asbestos is not used or is greatly reduced. , relates to an inexpensive vinyl chloride resin tile that can substantially eliminate pollution problems caused by asbestos.

``Prior art'' ``Problems to be solved by the invention'' The main component of polyvinyl chloride resin tiles is polyvinyl chloride resin, in which plasticizers and binders are used together, and heavy carbon dioxide is used as an extender. Calcium is contained, and precipitated calcium carbonate is sometimes used as a white gloss smoothing agent and surface strength improver.

In order to provide sufficient strength, the main ingredient is vinyl chloride.

Neil needs to be at least 25i1% by weight, and generally more than 3(1% by weight) is used.Such tiles are called homogeneous vinyl tiles, and JIs standards have been established, but vinyl chloride is expensive. Therefore, it is treated as a luxury item.

Therefore, on the other hand, the amount of vinyl chloride is 22f.
! % or less, generally 10 to 15% by weight. Semi-hard or soft vinyl asbestos tiles, which are also JIS standardized, are manufactured in large quantities. Although this is a low-grade product, it has the excellent advantage of being inexpensive.However, the amount of vinyl chloride resin is reduced, but the amount of extender pigment is higher, and since this extender pigment has no strength effect, the decrease in strength is is supplemented with asbestos.

However, as asbestos is a fine fibrous inorganic substance, in recent years it has suddenly become a major social problem in terms of occupational health and environment, such as the onset of silicosis due to dust. There is a need to develop technology that eliminates the need to use it at all.

Physical properties that pose problems with PVC tiles include length change due to water absorption, thermal expansion, denting, loss on heating, and chemical resistance. Uneven force applied to square tiles, such as by holding the edges of square tiles, often leads to breakage, so there has been a strong demand for improved strength in recent years.

In addition to strength issues, there are also major manufacturing process issues.

That is, since the manufacturing method is to knead the necessary ingredients, roll it, take it out in a continuous sheet form, and cut it into rated dimensions to make tiles, adhesion to the rolls is required.

As mentioned above, vinyl asbestos tiles have a small amount of vinyl chloride resin (because they use a large amount of an extender called heavy calcium carbonate as an extender, they have poor adhesiveness, and they also contain a large amount of asbestos). There is a disadvantage in the manufacturing method that the adhesion is inhibited and low @ production is not possible.Therefore, in order to improve processability, a copolymer with vinyl acetate is used instead of straight vinyl chloride polymer. However, it is preferable not to use vinyl acetate in terms of cost and physical properties.

Asbestos tiles have additional aesthetic drawbacks.

That is, since fibrous asbestos is used, the surface smoothness of the product is poor.

Heavy calcium carbonate is used as an extender pigment.
It is made into low layers by physically crushing and classifying natural limestone.

On the other hand, precipitated calcium carbonate is produced by reacting water with CaO, which is obtained by calcining natural limestone at high temperatures.
2 and reacted with 002 to chemically form CaCO3.
It is made by precipitating , has a narrow particle size distribution width, allows adjustment of the average particle size, has a crystalline shape with uniform particle size, and is well activated. This precipitated calcium carbonate is used as a homogeneous type as it has undergone surface treatment, but its strength is sufficiently guaranteed by the vinyl chloride polymer as the main component, so as mentioned above, it has white gloss, surface It is used only to improve smoothness and workability.

As mentioned above, PVC resin tiles are
It is roughly divided into two types, one is homogeneous type and the other is asbestos type, which is under the two major series, JI
The main ingredients are a straight polymer of PVC, the latter a copolymer of vinyl chloride and vinyl chloride, and heavy calcium carbonate as a filler, and precipitated calcium carbonate as a smooth white brightening agent. The asbestos type binder and other colorants, plasticizers, etc. are commonly used, but the asbestos type differs greatly in that asbestos is used.

The present inventors discovered that the above-mentioned asbestos type adhered to the roll,
We conducted repeated research to improve the adhesiveness and strength of the homogeneous type, and the results were first published in a patent application filed in 1983.
No. 154381 and No. 59-9358, but in the course of these studies, satisfactory results could not be obtained even by using heavy calcium carbonate surface-treated with natural resin acid. However, as a result of continued intensive research, it was discovered that natural resin acids have a softening point of 170°C or higher.
10 achieved by mechanical grinding using a Henschel mixer etc.
We discovered that it does not melt sufficiently at around 0℃, and that this is due to insufficient surface treatment.If we could overcome this problem, surface-treated heavy calcium carbonate would be able to have the same strength as asbestos. It has been found that adhesion to rolls, tackiness, white gloss and smoothness can be sufficiently satisfied.

``Means for Solving the Problems J'' The present invention provides a third type that does not use asbestos at all or has a reduced amount of asbestos, yet has strength equal to or greater than that of the asbestos type, and has extremely good processing performance. The object of the present invention is to provide a polyvinyl chloride resin tile which can also be referred to as a surface-treated heavy calcium carbonate type or isotype.

That is, the content is a polyvinyl chloride resin tile containing 22% by weight or less of vinyl chloride resin and 2 to 20% by weight of surface-treated heavy calcium carbonate.

The polyvinyl chloride resin tile of the present invention is made by impregnating the main component, vinyl chloride resin, with a plasticizer, increasing the weight with an extender such as heavy calcium carbonate, and reinforcing it with surface-treated heavy calcium carbonate. There is no problem in using a small amount of these together, and a binder may be added to improve processability during the manufacturing process. In addition, stabilizers and colorants are also used.

In the present invention, the main component vinyl chloride resin is 22ii
% or less, surface treated heavy calcium carbonate is 2-20! l
If the amount of surface-treated heavy calcium carbonate added is less than 2% by weight, sufficient strength will not be imparted;
If it exceeds A, the cost will increase and the strength of the product tile will tend to decrease. There are various grades of frI calcium carbonate depending on the degree of crushing and classification. These differences can be determined by the specific surface area (constant pressure aeration method), particle size distribution (light transmission method), etc. Specifically, the specific surface area is 2000
~3000cd/g coarse particles to specific surface 4
There are various types, including those as fine as 140,000 (III/g or more).

Generally, when dry grinding is used, a micron grinder, a vibrating ball mill, etc. are used, and when wet grinding, an SC mill or the like is used. Wet pulverization is better for obtaining particles with a large specific surface area and a narrow particle size distribution. 0 Surface treatment used in the present invention M1'! Calcium carbonate can be produced either dry or wet.

The surface treatment agent for these heavy calcium carbonates is not particularly limited and can be done by a known method. , paraffin, etc., which have a melting point below the temperature reached by mechanical grinding such as a Henschel mixer, and these may be used alone or in combination. Examples of modified resin acids include those in which the melting point has been lowered by making them soluble with Na, and those whose melting point has been lowered by esterification. In the case of natural resin acids, the melting point is too high, and it is necessary to use them together with those with a low melting point.For example, when performing surface treatment on a slurry of wet-pulverized heavy calcium carbonate, it is necessary to use soluble metal salts, etc. Although it is said that it is preferable to leave the powder in the form of an emulsion using an emulsifier, it is also possible to dry-process the powder directly.

The surface treatment obtained in this way! ! For example, put the ingredients to which heavy calcium carbonate has been added into a Banbury mixer, and mix 8
It's a high temperature condition of 0 to 180℃! ! The mixed wire is poured into a mixing roll made of two rotating bodies with an appropriate gap that rotate in opposite directions, and is formed into an annular zone with a certain thickness on the surface of the rotating body, which also serves as a layer of mixed wire. The annular zone is cut at 1 locations to take out a linear zone, which is rolled through a calendar roll to be thinned and formed into a sheet, which is then cooled and cut into predetermined dimensions to form a regular tile product.

During this process, the surface-treated heavy calcium carbonate particles, whose viscosity has been increased, adhere well to the mixing roll and are susceptible to further cross-contamination.The particles of the surface-treated heavy calcium carbonate have surface treatment agents adsorbed as a surface layer. and has high dispersibility.
Therefore, it is well dispersed in the polymer and is in a state of strong dispersion bonding with the polymer, giving great elasticity to the entire polymer and exhibiting excellent reinforcing properties.

In addition, because it has high dispersibility, it does not inhibit the viscosity of the polymer.
Therefore, it has the effect of replacing adhesives or reducing the amount of adhesives. It also has the advantage of being able to lower the temperature of the process.Furthermore, in asbestos type products, asbestos has oil absorption properties, and the plasticity of DOP, DHP, etc. is adsorbed by asbestos, inhibiting the plasticity effect. Since the product may be free of asbestos or have low amounts, the amount of plasticizer can be reduced.

Surface-treated heavy calcium carbonate is well dispersed, so
In addition to the above-mentioned adhesive effect and reinforcing effect, it also has excellent white gloss and smoothness, as is conventionally known.

Patent application No. 58-154381 proposed by the applicant,
As described in No. 59-9358, surface-treated precipitated calcium carbonate is effective as a substitute for asbestos in asbestos tiles.

However, surface-treated heavy calcium carbonate has the advantages of lower oil absorption, better dispersibility, and generally lower manufacturing cost than surface-treated precipitated calcium carbonate.
! If the amount of oil is low, the amount of plasticizer will be excessive with the same amount of plasticizer.
This amount softens the tile and consequently increases its strength.

In addition, since the surface of heavy calcium carbonate is inert compared to precipitated calcium carbonate, there is almost no secondary aggregation between particles, so it exhibits superior dispersibility compared to precipitated calcium carbonate, and this dispersion As a result, the strength of the tiles improves. In addition, considering the manufacturing cost, precipitated calcium carbonate is produced by igniting limestone and decomposing it into CaO and CO2.

is quenched with Hρ to become Ca(OH)2, and this Qa(O
H) React 2 with 002 to produce CaCO3.

On the other hand, since heavy calcium carbonate is made fine by mechanical crushing, there is a large difference in cost. Even if it is wet-milled and dried into a powder, it is cheaper than precipitated calcium carbonate.Therefore, if surface-treated heavy calcium carbonate is used as an asbestos substitute for asbestos tiles, it will be as effective as or better than precipitated calcium carbonate. Therefore, there is a large cost advantage. Furthermore, surface treatment of heavy calcium carbonate having a large specific surface area, that is, a small particle size, is better in terms of tackiness, strength, etc. than surface treatment of heavy calcium carbonate having a small specific surface area.

Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited by these in any way.

Example 1 m using a micron crusher and vibration mill! 1t.

10 kg of heavy calcium carbonate having a specific surface area of 25,000 cmi/g and 300 kg of resinate were mixed using a Henschel mixer. This sample was tested with the following formulation. The results are shown in Table 1.

The method for manufacturing and testing the sample tiles is as follows.

Compound: PVC resin tooiiffi part (Kaneka MB-1008) Surface treated heavy calcium carbonate 60 heavy calcium carbonate 600 DHP
35 binder
4- (Stabilizers, colorants, etc. were omitted.) Method for preparing sample tiles: The above formulation was heated at 100 to 150 for 5 minutes on a small test roll.
After kneading at ℃, it was made into a 30x30
It was taken out as a tile piece of d.

Test method: Strength test: In a constant temperature room adjusted to 3°C, a 50 g iron ball is dropped from a height of 1.5 m onto the above test tile piece placed horizontally on the floor to determine the state of crack occurrence.

Roll tack property: Determine the adhesion of the compound to the roll (I adhesion) during kneading with a mixing roll.

Cohesiveness: Judged by the time required for the compound to cohere uniformly when kneaded.

Thermal stability = Heat the tiles at 180°C for 50 minutes with the gear open and judge by the presence or absence of discoloration.

Comparative Example 1 A test was conducted in the same manner as in Example 1, except that untreated ground calcium carbonate was replaced with surface-treated ground calcium carbonate. The results are shown in Table 1.

Comparative Example 2 A test was conducted in the same manner as in Example 1 except that the surface-treated heavy calcium carbonate was replaced with asbestos and 16 parts by weight of a binder was added. The results are shown in Table 1.

Table 1 (Note) O: Good Δ: Slightly poor ×: Poor “Effect” “
Effects of the Invention The present invention is a surface treatment that is a substitute for all or some percentage of asbestos! Since i'R calcium carbonate acts as a reinforcing agent, it is possible to provide a new type of tile with strength equal to or greater than asbestos-containing tiles. Moreover, surface-treated heavy calcium has excellent caking properties in the manufacturing process, can be manufactured at low temperatures, and can replace expensive caking agents or reduce the amount of caking agents used. Therefore, compared to asbestos-type products, it not only can reduce costs, but also has the effect of killing two birds with one stone, in that it can overcome environmental health problems caused by asbestos.

Procedure-? Masashi-1- (spontaneous) 1. Indication of the case Patent Application No. 151548 filed in 1982 2. Name of the invention Polyvinyl chloride resin tile 3. Person making the amendment Relationship with the case 2. Address of the patent applicant Akashi, Hyogo Prefecture Address: 455 Nishioka, Ichiuozumi-cho Name: Kyuubi Calcium Co., Ltd. Representative Director and President: Rinbe Kyuo 4, Agent address: 3-2 WtA, No. I1g, Nishitenma, Kita-ku, Osaka "Detailed description of the invention" section of the repair oath The description of ``r300kgJ'' will be corrected as follows; ■ On page 12 of the specification, at the bottom, ``r300kgJ'' will be changed to 1
Corrected to 300g.

that's all

Claims (1)

[Claims] 1. The vinyl chloride resin content is 22% by weight or less,
2-20% by weight of surface-treated heavy calcium carbonate
A polyvinyl chloride resin tile containing 2. The resin according to claim 1, which is surface-treated with at least one selected from resin acids, fatty acids, fatty acid esters, petroleum resins, coumaron resins, ABS, and paraffins in which heavy calcium carbonate is modified. tile.