TW593201B - Lightweight clay and manufacturing process thereof - Google Patents

Abstract

The present invention relates to a lightweight clay, which is easy in being formed according to a specified shape, having a suitable storage property, and a low production cost, and a method for producing the same. The invented lightweight clay contains an organic hollow micro-capsule, and a binder resin. The organic hollow micro-capsule has an average particle size of 15 to 150 mum and an addition content of below 6 wt%. Furthermore, the lightweight clay has a whiteness (WL) of more than 50 when measured according to JIS L 0803.

Description

593201 V. Description of the Invention (i) [Field of the Invention] The present invention relates to a lightweight clay and a method for manufacturing the same. The invention relates to a kind of clay which has suitable lightweight performance or modeling performance, has many excellent properties, and has low manufacturing cost. Lightweight clay and its manufacturing method. [Previous technology] At present, the clay used in arts and crafts or school textbooks is mainly composed of granular plains and hawthorn remains as disintegration materials. The material is added to the material to bind granular materials. It is composed of additives such as agents, fragrances, pigments, and oil. Therefore, the conventional point soil has the disadvantages of heavy dead water and inconvenient use. For this reason, in the official gazette No. 51 ~ 893, you have disclosed that the foamed polybenzyl methacrylate is a nasal master and the ancestral ancestral descent; light weight stickiness constituted by knives: paper is added to the material襞 Material or aquatic: In terms of its structure, the surface of polystyrene is very water-soluble and even liquid-containing:: Tong, and so on, there will be a rich, strong and powerful $ X41. In the same way, the overall weight of lightweight clay still exists. There is also a lot of unloading..., 孖 is not easy to be miniaturized .: 屮 挂 ί and 'Because of foaming polybenzyl, in addition, it will be published in the series ^ and The formulation materials are all mixed and mixed. 30 to 100% of the powder and granules (the granulated knife, &, a small hollow 13% weight unit composed of organic materials, & 〇_, the volume specific gravity is 0.6 or less ), 3 ~ (weight percent) Ά; degree is below 15Mm), 3 ~ 8%, after a single agent or combined agent of water & paste, and

Page 4 (weight percentage, fiber length / length is 1G_ or less), 31 ~ 60% 593201 V. Description of the invention (2) · Water mixing: 'The penetration can be polished by adjusting the penetration to 1 0 0 to 3 5 0 Forming clay. In addition, a sculpture material similar to this structure is also disclosed in Japanese Patent Publication No. 5-7-1636. However, the forming clay or sculpture material is not easy to mix and disperse because the amount of tiny hollow powder particles or rock powder made of rhenium foamed inorganic material is large, and the obtained forming clay or sculpture material is not only Lack of operating performance or styling performance, and its manufacturing cost is still high. In Japanese Patent Application Laid-Open No. 2-123390, organic hollow microspheres (the outer shell of which is composed of a copolymer containing vinylidene dichloride or even acrylonitrile, accounting for 3 to 20% by weight based on the total weight) are disclosed. Composition), too

5 ~ 20% by weight of synthetic binder (carboxymethyl cellulose), 10 ~ 30% by weight of fiber powder, and 50 ~ 60% by weight of water, and click here Lightweight, white, and light-weight clay that is easily blended in proportion. That is, when the formula ratio of the organic hollow microspheres is less than 3% (weight percent), the predetermined target weight cannot be reached; and when the formula ratio of the organic hollow microspheres exceeds 20% (weight percent), Damage to the properties of lightweight clay. In addition, when the formula ratio of the fiber powder is less than 10% (weight percentage), the role of the bonding material cannot be fully exerted; and when the formula ratio of the fiber powder exceeds 30% (weight percentage), a large amount will be saved due to storage. Water and damage to the lightweight of the clay. When the formula ratio of water is less than 50% by weight, the molding operation will be difficult; when the formula ratio of water exceeds 60% by weight,

593201 V. When the invention (3) '‘, it will soften the clay and cause lack of modeling performance, and it will also damage the lightweight of the clay. However, when the amount of the organic clay microspheres added exceeds 20% (weight percent) of the maximum weight of the lightweight clay, the mixing and dispersion of the organic hollow microspheres will be affected, and the resulting clay will be too light and lack operating performance. Or modeling performance, and increase manufacturing costs. The light-weight clay, because of the large amount of organic hollow microspheres added, tends to leave foaming gas (foaming liquid), which is the so-called unfoamed organic hollow microspheres. Therefore, when the lightweight clay is covered with packaging materials such as polyethylene film and stored for a long time, or when the surrounding temperature rises in summer and other high temperature conditions, there is a residual foaming gas, so the lightweight clay covered by the packaging material Will expand to about 1.2 to 3 times the initial volume (hereinafter referred to as the expansion problem). Green In addition, the light-weight clay has a large number of organic hollow microspheres. When pigments are added, there is a problem that the pigments are prevented from being dispersed and good color development performance cannot be obtained. Japanese Unexamined Patent Publication No. 10—2 6 8 7 5 5 discloses glass micro hollow spheres (having a particle size of 1 to 2 0 / zm), 30 to 60 by a unit of 30 to 70 weight. Fiber powder in weight units, methyl cellulose in the range of 10 to 50 weight units, and water in the weight range of 200 to 400 weight units (based on the total weight of glass micro hollow balls, fiber powder, and carboxymethyl cellulose) ) To obtain a lightweight clay with short drying days and small shrinkage. In other words, when the proportion of glass microspheres is less than 30 weight units, the weight of clay cannot be achieved.

593201 V. Explanation of the invention (4) • For example, when the weight exceeds σσ at the early stage, 5 the clay is easy to shrink and crack, and when the proportion of the fiber powder is less than 30 weight ασ, the shrinkage or crack of the lightweight clay is at the early stage. It will increase y. When the formula ratio of fiber powder exceeds 60 weight, the weight of water will be affected due to the preservation of a large amount of water. In addition, when the formula ratio of water is less than 200 weight units, it will be a light clay. Difficulties in modeling operations 1 When the formula ratio of water exceeds 400 weight units, it will soften the clay and lack modeling, and it will easily adhere to the hands. 0 The lightweight clay mentioned in the paper is due to glass hollow microspheres or fiber powder. Addition of an excessive proportion of clay lacks modeling performance and the manufacturing cost is still low. Moreover, the lightweight clay is In addition, because the amount of hollow glass microspheres is too much, when pigment is added, the pigment dispersion will be hindered, and the method yields a good% :: color performance 〇N% For this reason, the inventors of the present invention Organic medium. The average particle size or whiteness (WL) of the empty microspheres and the amount of addition have been studied and found to be involved in its interaction. 5 Affects the whiteness (WL) of lightweight clay. Hair coloring performance. Modeling performance%. Lightweight. The relationship between performance and swelling problems 0 The object of the present invention is to provide a hair coloring performance styling performance Λ excellent lightweight performance 1 even if stored in a state covered by packaging materials for a long period of time or the ambient temperature rises in summer, such as summer, Jida / JEL Lightweight clay with good storage performance Λ that does not swell under conditions and cheap production cost and its production Method of making

593201 V. Description of the invention (5) [Summary of the invention The resin of the present invention is within the range of the total weight; and, the value of 50 is within the range of 50, and the appearance and color performance are high. In addition, it is small, so that it can interfere with the existing (20% by weight, so not only can it be obtained with the amount of easy mixing and dispersion; and, the amount of light weight clay of the present invention, which contains organic hollow, which has production costs The average particle diameter of the microspheres and the organic hollow microspheres of the binder is set to 15 to 150 β m, and the amount of the organic hollow microspheres to be added is set to a range of 6% (weight percent) or less. The value is based on the whiteness (WL) of light weight clay measured according to JISL 0 803. When the average particle size of this organic hollow microsphere is controlled to a certain range, by controlling the whiteness (WL) of light weight clay, It can be mentioned that when adding pigments for coloring, you can get excellent results. Even if you add more technical percentages to get good machine hollow, you can also reduce the light viscosity of the excellent inventions with added pigments. )) In comparison with the amount of hollow microspheres added in the microspheres with the expected performance of the microspheres, the dispersion performance of the pigment will not be reduced. Talent performance. Organic hollow microspheres of soil are added ‘the amount of the present invention is reduced by a large amount and sufficient weight is reduced, and the clay is lightweight. The addition amount is small, not only the lightweight clay, the existence of foamed organic hollow microspheres, but also the enabling (expanding performance) of expensive organic hollow microspheres.

Limited to another form of low to medium

593201 V. Description of the invention (6) The average particle diameter of the hollow microspheres of light clay of balls and binder resin is 15 (the addition amount is 6% (weight percentage) below); meanwhile, the organic "Kneading" makes the value measured in accordance with J IS L 0803 (WL) be 50 or more. In this way, a light-weight clay with superior manufacturing quality can be obtained. [Introduction of the invention] The embodiment of the present invention is a binder resin and a fiber manufacturing method containing a compound composition. Relative to 6% (weight percent) or less, and the whiteness (WL) of the soil is 50 or less, the organic hollow microspheres will be described. 1 · Organic hollow microspheres (1) Type 1 As long as the organic hollow microspheres use microscopic shells with voids inside, as the organic hollow microspheres, acrylonitrile copolymer resin, vinyl ethyl acrylate acrylic resin copolymer The manufacturing method, wherein the value within the range of ~ (relative to the overall weight of the hollow microspheres and the light weight clay produced by the binder, the white type performance, light weight, and organic hollow microscopic fine with excellent color development The average particle size of the light sticky ball, yam, water, and pigment is set to 15 body weight. It is added organically measured in accordance with JIS L 0 8 0 3? The amount of addition and the resin progresses whiteness performance. Polarized soil The components of light green and polar compounds can be made of organic materials. The outer shell can be composed of sub- (diester acrylonitrile copolymer resin acrylic fine nitrile resin, etc.) outside the gas ethyl, methyl package

593201 V. Description of the invention (7) Organic hollow microspheres with gas or liquid. Among the 14 organic hollow microspheres, especially the organic hollow microspheres with a shell made of a di-acrylonitrile copolymer resin, it is easy to say that when heated, it can also be used for heating. ^ J ~ ^ M 便% 版To the desired size, it is ideal. But 疋, organic hollow microspheres made of sub-(-) decay / more + ^ 丄 ..., a) gas ethylene acrylonitrile copolymer resin, in the case of Christine, sentence 眇 A ,, w a 4 4 In the package, the temperature may be high or the temperature distribution may be uneven. It is necessary to pay attention to the color of brown or brown, so that the right (WL) does not reach 50. Factory, — by vinyl acetate propylene, said # #… &, ^ ^, ^ N Nitrile Copolymer Resin, Methyl Methacrylate Acrylonitrile Copolymerization MM, Acrylonitrile Volume {_〆 望 生Shuyue Yue and other organic hollow microspheres, which form the outer shell, have a whiter performance than their ^ r, ^, so it is easier to adjust the whiteness (WL). (2) Type 2

In addition to organic hollow micro-broken wro ^ r, 5ί,, ^ clothing, you can also use the shell as a material (for example, glass hollow material ^ ΛΑ-UU ^ inorganic hollow microspheres. Chemical inorganic hollow and f ^ , ^ TRnnc * Μ · Small ball, colorless and transparent, high compressive strength, for example, 'lkgf = 9.80 7N / cm2) ^^ So, s, card + ^% storage rate is 90 ~ 92 (VOL%), and Lighter. Therefore, through the use of organic intermediary, the weight per unit volume of the organic hollow microspheres while simultaneously reducing the _ / ^ attacking ball and the inorganic hollow microspheres is significantly reduced. At the same time, the role of the buffer material, that is, the thermal mechanical hollow microsphere The surrounding, played a role in improving the inorganic hollow * 1u effectively prevent the inorganic hollow microspheres from suffering from the wide dispersion of organic hollow microspheres and spheres. 1 simultaneous use of hollow microspheres

In terms of its relationship with pigments, it can maintain the shape retention performance, reduce shrinkage = color development performance, and improve lightweight clay. In addition, through the use of organic hollow micro; use, can relatively reduce organic and inorganic hollow microspheres while preventing The amount of foamed organic hollow micro ^ micro + spheres is used, so that the storage performance is more effective. One Λ ', the expansion problem caused by the ball, the color of the organic hollow microspheres with excellent (3) whiteness is obtained, which is good, that is, according to j I s L 〇8 〇3-said color or color close to white should be Values above 50. "疋, organic hollow microspheres have whiteness (WL). The reason is that the whiteness of the lightweight clay () and the coloration performance of the light clay are more excellent when various whites with a chromaticity (WL) of 50 or more are white. When the degree of lightness (WL) is less than 50, the color will decrease when a pigment or yellow pigment is added to the light 2: clay. However, if the whiteness (WL) is a hollow microsphere, it is a constituent material. Therefore, the organic hollow is preferably within the range of 99.9. In addition, the whiteness (WL) value of the microspheres is added to the extra space of the oxide microspheres. Organic hollow microballoons can be adjusted 'or can be added with lightweight clay; on the contrary, if the so-called' organic hollow microballoons are slightly theophylline ', especially the phenomenon of white cloudiness is added at the same time, its color development performance is obvious If the value is too high, the whiteness (WL) of the microspheres will be excessively limited to a value in the range of 70 to 9 9. It is better to adjust the 'by white particles such as organic hollow or one gasification fragmentation, or

593201 V. Description of the invention (9). The method of "the person" is covered with these white particles; in addition, it can also be achieved by lowering the vinyl chloride resin or sub (di) vinyl chloride resin on the shell of the organic hollow microsphere, or The amount of formaldehyde resin (phenol resin, melamine resin, melamine resin 'urea resin), etc. can be used to achieve it. Specifically, the amount of use is set to a value of not more than 0% by weight That is, it can also be achieved by adding or coating a fluorescent color enhancer described later in the shell of the organic hollow microsphere. The whiteness (WL) of the organic hollow microspheres and the whiteness (WL) of the lightweight clay described later can be measured according to J IS L 0 8 0 3, and more specifically, a reflectance meter (such as · TR-1000D type or TC-1800MK2 manufactured by Tokyo Denshoku Corporation. (4) Average particle size 1 The average particle size of the organic hollow microspheres should be in the range of 15 to 15 0 // m. The reason is that if the value of the average particle diameter of the organic hollow microspheres is not more than 1 5 // m, the modeling performance or whiteness (WL) of the lightweight clay will be reduced, or it will be added in a predetermined amount. It is difficult to achieve weight reduction. On the other hand, if the value of the average particle diameter of the organic hollow microspheres exceeds 150 / z m, it is difficult to mix and disperse, or problems such as low modeling performance of lightweight clay occur. Therefore, the value of the average particle diameter of the organic hollow microspheres is more preferably in a range of 50 to 130 / zm, and most preferably in a range of 70 to 120 // m. The average particle size of the organic hollow microspheres can be obtained through an optical microscope.

593201 V. Description of the Invention (ίο)-An image of a hollow ball in a machine, and then calculate this image using a day image processing device. (5) Average particle diameter 2 When determining the average particle diameter of the organic hollow microspheres, it is desirable to consider the average particle diameter of the pigment described later. That is, when the average particle diameter of the pigment is D 1 and the average particle diameter of the organic hollow microspheres is D 2, the ratio of D2 / D1 is suitably within the range of 10 to 50, 0, 0, 0. The reason is that when the ratio of D2 / D1 is less than 10, the pigment is not uniformly dispersed, thereby affecting the color development of the organic hollow microspheres. On the other hand, when the ratio of D2 / D1 exceeds 50,000, the pigment is easy to coagulate, and at the same time, it does not disperse uniformly, thereby reducing its color development performance. Therefore, in order to improve the color development performance of the pigment, the D 2 / D 1 ratio is preferably in a range of 50 to 10, 0 0 0, and in a range of 1 0 to 1, 0 0 0 Within the value is better. Qian Fen (6) Adding amount The adding amount of organic hollow microspheres is set within the range of 0.1 to 6% (weight percentage) relative to the total weight. The reason is that when the amount of the organic hollow microspheres added is less than 0.1% by weight, it is difficult to reduce the weight of the lightweight clay. On the other hand, when the amount of the organic hollow microspheres added exceeds 6% by weight, the modeling performance or handling performance of the lightweight clay will be reduced, and at the same time, the remaining unfoamed organic hollow microspheres will change. In this way, it should be covered with packaging materials for long-term storage, or

Page 13 593201 V. Description of the invention (11) · When it rises, the packaging material will swell, which will significantly reduce its storage performance. In addition, because the price of organic hollow microspheres is particularly high, when the added amount exceeds 6% by weight, the cost of the obtained lightweight clay will also be high. Therefore, in order to achieve a good balance between the modeling performance or swelling performance of the lightweight clay and the lightness, the addition amount of the organic hollow microspheres is more preferably within a range of 0.5 to 4% (weight percentage), The best value is in the range of 1% to less than 3% (weight percent). In addition, the amount of organic hollow microspheres should consider the density of the binder resin, that is, determine the density of the organic hollow microspheres by considering the density of the binder resin. The added amount of balls can finally provide lightweight clay with equal density and economy. More specifically, when the density of constituent materials other than the organic hollow microspheres is 0.5 to less than 0.8 g / c m2, the amount of the organic hollow microspheres added is 1% to the total weight. When the density is less than 3% (weight percentage), the constituent materials other than the organic hollow microspheres have a density of 0.8 to 5g / cm2, and the organic hollow microspheres are added in an amount relative to the entire weight. Within the range of 0 · 1 to 6% (weight percent): Good. Here, the relationship between the addition amount of the organic hollow microspheres and the lightweight performance, modeling performance, swelling performance, and manufacturing cost of the lightweight clay will be described in detail with reference to FIGS. 1 to 3 respectively. FIG. 1 is a numerical calculation of the data of the lightweight performance and the styling performance of Table 1. The numerical calculation is based on 5 points for ◎, 3 points for ◦, 1 point for △, and 0 point for X. from.

Page 14 593201 V: Description of the invention (12) The horizontal axis in Figure 1 represents the amount of organic hollow microspheres added (% (weight percentage)); the left vertical axis represents lightweight performance (relative value), and the curve A represents its relationship . In addition, the right vertical axis in FIG. 1 indicates the molding performance (relative value), and the relationship between the amount and the addition amount (% (weight percentage)) of the organic hollow microspheres is indicated by a face line B. According to the characteristic curve shown in FIG. 1, it can be understood that the more the amount of organic hollow microspheres added, the higher the evaluation of the lightweight performance of lightweight clay. Therefore, in order to obtain appropriate lightweight performance, organic hollow microspheres The amount of balls added must be at least 0.1% by weight. On the other hand, for the modeling performance of lightweight clay, the amount of addition begins to decrease extremely at the limit of 3% (weight percent), and decreases to 1 when it reaches 5% (weight percent), and it evaluates when it reaches 7% (weight percent). Almost reduced to 0. Therefore, by setting the addition amount of the organic hollow microspheres within a range of 0.1 to 6% (weight percent), a good balance is achieved between the lightweight performance and the modeling performance of the obtained lightweight clay; moreover, If the amount of the organic hollow microspheres is in the range of 1% to less than 3% (weight percent), these properties will have a superior balance. Figure 2 is a digitized calculation of the swellability data in Table 1 with digits of 5 for ◎, 3 for ◦, 1 for △, and 0 for X. The horizontal axis of Fig. 2 represents the amount of organic hollow microspheres added (% (weight percentage)), and the left vertical axis represents the expansion performance (relative value). According to the characteristic curve shown in FIG. 2, it can be understood that the more the organic hollow microspheres are added, the lower the expansion performance; more specifically, the

Page 15 593201 V. Description of the invention (13), the amount of addition begins to decrease extremely at the limit of 3% (weight percent), decreases to 1 at 5% (weight percent), and the evaluation is almost reduced at 7% (weight percent) To 0. Therefore, based on the results shown in FIG. 1 and FIG. 2, if the amount of the organic hollow microspheres is in the range of 0.1 to 6% (weight percentage), the lightweight performance and modeling performance of the lightweight clay, There is a good balance between storage and swelling during storage: and if the amount of organic hollow microspheres is in the range of 1¾ to less than 3% (weight percentage), it is more superior for this characteristic. In addition, Figure 3 shows the relationship between the amount of organic hollow microspheres added to lightweight clay and the cost ratio of lightweight clay. When the amount of organic hollow microspheres added is 2% by weight, The cost of lightweight clay is based on 100%. From the characteristic curve shown in Figure 3, it can be understood that with the increase of the amount of organic hollow microspheres added, the cost ratio of lightweight clay will increase, especially when the amount is 6% (weight percent). This is the beginning of an extreme rise in the industry. When the amount is 6% (weight percent), the cost ratio rises to 150%, and when the amount is 7% (weight percent), the cost ratio is 220%. Therefore, based on the results shown in Figs. 1 to 3, since the amount of the organic hollow microspheres is in the range of 0 · 1 to 6% by weight, the light weight performance or modeling performance of light clay, There is a good balance between the cost ratio, and if the addition amount of the organic hollow microspheres is in the range of 1% to less than 3% (weight percentage), it will be good for this characteristic.

Page 16 593201 V. Description of the invention (14) Better balance. (7) Bulk density The bulk density of the organic hollow microspheres is preferably within a range of 0.001 to 0.5 g / cm3. The reason is that if the bulk density of the organic hollow microspheres is less than 0.001 g / cm3, it is difficult to uniformly mix and disperse them in lightweight clay. On the other hand, if the bulk density of the organic hollow microspheres exceeds 0.5 g / cm3, the ductility of lightweight clay will be reduced, or the lightweight clay of lightweight clay will be affected. Therefore, the bulk density of the organic hollow microspheres is more preferably in the range of 0. 0 0 5 to 0.2 g / cm3, and most preferably in the range of 0.01 to 0. lg / cm3. The bulk density of the organic hollow microspheres can be measured in accordance with J I S K 5 1 0 1 (pigment test method). (8) PH value The PΗ value of the organic hollow microspheres should be in the range of 3 to 11. The reason is that if the pH value of the organic hollow microspheres is less than 3, gelation will occur when a hydroxyl-containing compound or a carboxyl-containing compound is added and stored for a long period of time. On the other hand, if the PH value of the organic hollow microspheres exceeds 11, the operation of mixing and dispersing or using them becomes difficult. Therefore, the PH value of the organic hollow microspheres is more preferably within a range of 6 to 1 0.5, and most preferably is within a range of neutral to weakly perceptual values of 7 to 1 0.5.

Page 17 593201 V. Description of the invention (15), (9) Surface treatment The surroundings of the organic hollow microspheres should be surface-treated with a fluorescent whitening agent described later. The whiteness (WL) of the spheres is lower than that of light brighteners. When the surroundings of lightweight clay pass through white particles into the hollow microspheres, the L value of the hollow microspheres through tritium tin, zinc oxide, and vulcanizing machine will have mechanical characteristics. There are also obvious improvements and treatment with Shishiyao coupler. The reason is that ^^ through the organic hollow microspheres uses fluorescent whitening agents in the range of 0 · 〇ι ~ 1% (when using white particles in weight percentage, the phase% weight is ^ ~~). In some cases, it can also be adjusted to a desired range by using a small amount of fluorescent L value ^ > 4 77, it is best to surface-treat the organic medium-sized micro 琰 仃. The addition of rhenium oxide and 1 ′ Γ is easy to adjust for organic zinc, oxides, and other oxides, and the same color particles make it high. T, its dispersibility or rhenium coupling agent, FF machine hollow microspheres When the Zhou coupling sword's coupling agent, etc., performs surface properties or mechanical properties y to significantly improve the relative surface treatment, if the value of tb) is in the range of: 纟, the added amount is 对于 for the whole. Similarly, if the amount of the 0 colored particles is added, the Capricorn circumference value of 4 is within the range of the name (heavy) 'in the overall weight df 0 summer cents) g, coupling agent. Polarized character range Better. The amount of addition should be in the range of 0.1 to 10, v, Wang. The amount of addition to be treated with a coupling agent should be in the range of 0.05 to 5%.

593201 V. Description of the invention (16) ‘* (1) Type As the extreme-performance compound of the binder resin, it is preferable to use, for example, a compound containing a hydroxyl group or a compound containing a condensed group. In addition, like polyacrylic acid or polyvinyl alcohol, both functional groups containing both a hydroxyl group and a carboxyl group are contained in the molecule, and they will be described separately for convenience. The hydroxyl-containing compound may be polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyvinyl acetate, urea resin, methyl cellulose, ethyl cellulose, hydroxy ester Cellulose and so on. By adding these warp-containing compounds, it is easier to adjust the extensibility or discoloration of lightweight clay. In addition, since these hydroxy-containing compounds are generally water-soluble compounds, even when water is added to a lightweight clay, excellent compatibility can be obtained. In particular, polyvinyl alcohol has a large amount of hydroxyl groups in each weight unit, so it can be used to improve the ductility or use effect of lightweight clay by a small amount of addition. It is a more suitable hydroxyl-containing compound. In addition, although polyvinyl formal or polyvinyl butyral is the result of acetalization of polyvinyl alcohol with formaldehyde or butyraldehyde, respectively, it will have superior resistance if used in lightweight clay. Fading performance or heat resistance. Although polyvinyl acetate is a raw material before saponification of polyvinyl alcohol, it is a very effective hydroxyl group-containing compound when it is desired to obtain a lightweight clay having more excellent spreadability. Carboxyl-containing compound

Page 19 593201 V. Description of the invention "(17)" The carboxyl-containing compound may be carboxymethyl cellulose (CMC), acrylic acid, polyvinyl acetate, or the like. Here, when using carboxymethyl cellulose, it is suitable to use carboxymethyl cellulose having an etherification degree in the range of 0.1 to 2 values. The reason is that if the degree of etherification of carboxymethyl cellulose is less than 0.1, light-weight clay will be sticky and difficult to use. On the other hand, if the test degree of carboxymethylcellulose exceeds 2, the ductility of light weight clay is reduced, and it becomes difficult to form a thin film. (2) Adding amount Relative to the total weight (100% (weight percent)), the addition amount of the extreme performance compound should be within the range of 0.1 to 30% (weight percent). The reason is that when the added amount of the polar compound is less than 0.1% (weight percentage), the handling performance or modeling performance of the lightweight clay will be significantly reduced. On the other hand, when the added amount of the extreme performance compound exceeds 30% by weight, the ductility of the lightweight clay is reduced, or it is dispersed by mixing. So, in order to have a good balance between the operating performance or modeling performance of lightweight clay and the ductility of lightweight clay, the amount of polar compounds added is 0% relative to the total weight (100% (weight percentage)). · A value in the range of 5 to 20% (weight percent) is preferred, a value in the range of 1 to 15% (weight percent) is more preferred, and a value in the range of 2 to 10% (weight percent) is optimal. 3Fiber

Page 20 593201 V. Description of the invention. (18) (1) The type of pulp used as an additive) There are no separate leaves and oblique leaves: (for wide materials. 4 Don't restrict 'suitable a: yes' #Use a broad-leaved tree The fiber used as the raw material is better = the dimensional stability of the leaf tree as the raw material and the coniferous fiber = the dagger .: Generally, the fiber with the leaf tree as the original family is shorter. (2) the average fiber length ^ ϊ average, the length is preferably within the range of 1 to 20, the value will cause the light fiber = flat fiber fiber length is less than 0. olmm On the other hand, When the average fiber length of the fiber is equal to 1%, it will be difficult to mix and disperse uniformly in the amount of clay. Long (Koruji Temple, in light, so in order to make the balance of light clay better, the fiber The average fiber length is within the range of 0. "Heart's energy", and the best value is in the range of 0.5 to 5 coffee. &%; Within the value% (3) Addition amount per fiber The amount should consider light weight energy, or consider the ease of manufacture of light clay fi or moldability. For the overall weight, it is determined by two, wide: = degrees. For example, phase The range is better, and the reason is 卩 1% ~ less than ln (weight percentage). When the fiber addition ratio is mentioned, the addition effect will not be exerted. Another iHU fractal dimension addition amount exceeds 10% (Weight percentage) Risi, it will be difficult to control the amount of light weight of Tian Zhijin: 593201 V. Description of the invention (19)... The ductility of the soil causes manufacturing trouble. Therefore, the amount of fiber added is relative to the whole. In terms of weight, a value in the range of 2 to 9% (weight percent) is more preferable, and a value in the range of 3 to 8% (weight percent) is the best. 4 · The amount of water and water should be considered The handling performance or molding performance of the lightweight clay, or the ease of manufacturing the lightweight clay are determined. For example, it is suitable to be in the range of 61 to 85% (weight percent) relative to the overall weight.

The reason is that when the amount of water added is less than 61% by weight, the effect of addition cannot be exhibited. On the other hand, when the amount of water added exceeds 85% by weight, it may be difficult to control the ductility or discoloration of lightweight clay. Therefore, the added amount of water is more preferably in the range of 65 to 83% (weight percent) relative to the total weight, and in the range of 67 to 80% (weight percent). For the best. Barrier 5Pigment (1)

The type of the pigment is not particularly limited as long as it can be used in inks, coating materials, etc. in the prior art. For example, organic pigments, inorganic pigments, or dyes. The organic pigments may be azo pigments such as azo lakes, insoluble azo pigments, polymeric azo pigments, chelated azo pigments, or m-cyanine pigments, forced coagulation pigments, unforced pigments, and anthraquinones. Dye, quinacrid

Page 22 593201 V. Description of the invention (20) materials, dioxin-based pigments, thioindigo pigments, color) pigments, etc., and other materials, such as Yinmu Lin Yan shaking, quinic acid _ (yellow, τ inch evening% Pigments, dye lakes, etc. As inorganic pigments, they can be iron oxides, iron oxides, iron oxides, chromium oxides, carbon blacks, iron oxide yellows, pearl pigments, etc.:) ... iron ... Lin condensation resin is breaking! ff: When adding fresh tint, it is suitable to use the non-molded plastics based on Fuma's organic dipropylene: acid resin, melamine resin, etc. as the base. The average particle diameter of sintering (2) such as sulfide, and the average particle diameter of ΓΓ are preferably in the range of 0.01 to 0.21 / π1. Obviously, Rongzong Rongshan, when the average particle size of the pigment is less than 0.01 factory 1 ", the phenomenon of coagulation is dispersed and it is difficult to mix uniformly in lightweight clay. Average particle size: it affects its color development performance. On the other hand, when the pigment is complementary to # 2, it cannot exhibit the% phase with the organic hollow microspheres. Therefore, the coloring performance of the lightweight clay is reduced. Good balance, in order to make the pigment's coagulation performance and color development performance more good, the average particle diameter of the pigment is in the range of 0.06 ~ 0.18 // Π1, and ^ 'is in the range of 0.07 ~ 〇 · The best value is within the range of 12 # πι. High, and if the particle size of the pigment is small, its surface activity will be improved. But t makes it easy to adhere to the peripheral microspheres of hollow microspheres with an average particle size larger than that. Even if the pigment is attached to the medium ratio | The light clay phase is less likely to interfere with external light. 593201 V. Description of the invention (21) " " A '------ f Here, referring to Fig. 6 (a) A (b), the average particle size of the pigment pigment is transparent (that is, the color performance) The relationship between them is explained in detail. Inside the machine is a schematic diagram of the relationship between the pigment 10 of the lightweight clay of the present invention, the hexamer Γ, and the external light 14,16. The picture shows the relationship between the pigments 20 of the lightweight clay of the prior art, the organic hollow microspheres 22, and the external light 24, 26. The schematic diagram is shown in Figure 6 (a). In the lightweight clay of the invention, since the main: "The value of the flat f particle diameter of! 10 is exactly the value of ^ of the wavelength of light with V? = In order to adjust the standard deviation of the particle size distribution to a predetermined range = ', so even The pigment 10 is attached to the hollow sphere 12 and covers the surroundings, and does not prevent the light 14 and 16 from transmitting. Now, the value of 、: In Fig. 6 'due to the average particle size of the pigment pigment 20', Cheng 2 ;: 5, or greater 'so the pigment pigment 20 adheres to the organic substrate 2 2 and covers it in the pot ^' through. 1 // 捋 around, will hinder the external light 24 ^ 26 So 'the lightweight point of the present invention is defined by organic hollow microspheres 12, and has a beast: people are full of thought / is by using special pigment 1 0 The combination can effectively prevent the organic hollow microspheres 12 from being scattered even if the color of the pigments such as the average grains is effectively dispersed, and it is enough to obtain more bright and transparent hair. The length is 12 and the standard deviation of the particle size distribution of the pigment can be measured by a + laser powder counter. Tian She can use (3) Particle size distribution 1 For pigment particle size distribution, the value below 1 square. ^ The quasi-deviation is suitable between 0.05 and 593201

V. Explanation of the invention (22) The reason is that when the standard deviation of the pigment exceeds 0.05, the light scattering will increase, or the obvious coagulation will easily occur and the color development performance of the pigment will decrease. However, if the standard deviation of the pigment is too small, the manufacturing cost for control will increase. Therefore, in order to well maintain the balance between the color development performance of the pigment and the manufacturing cost, the standard deviation of the particle size distribution of the pigment is more preferably in the range of 0.0 · 4 ~ 〇 ♦ 0 丨 β 01, with a range of 0.03 ~ 0.01 // in is the best value. (4) Particle size distribution 95% of the particle size of the pigment is preferably within a range of ± 10% of the average particle size. By using a narrow particle size distribution like this, the reason is: Come: at a light weight with excellent color and styling properties, in reverse, 95% of the particle size of s pigments exceeds 1 n. L ·; , Which affects the play of the organic 3%. Therefore, # pigment particle size fraction # = the complementarity of microspheres will decrease. 3, the color development of the pigment is therefore 'in order to obtain an excellent pigment, the range of color range of ± 8% of the average particle diameter is within the range of ± 5% of the average particle diameter. good. The internal content is more preferable to exist. In addition, for the pigment flat particles, a 95% particle size distribution that can be performed by a laser-based powder counter, (5) The amount of addition is determined. "

593201 V. Description of the invention (23) ′. Relative to the total weight, the added amount of the pigment is preferably in the range of 0.001 to 1% by weight. The reason is that when the added amount of the pigment is less than 0. 0 丨% (weight percentage), the added effect or the complementary effect with the organic hollow microspheres cannot be exerted, and the color development performance is also reduced. On the other hand, when the pigment is added in an amount exceeding 10% by weight, its light scattering becomes large, or obvious coagulation occurs, thereby reducing its hair island performance. " " Therefore, in order to make the color performance of the pigment better, the amount of pigment added is more preferably in the range of 0.05 ~ 8% (weight percent), so as to be in the range of 0.5 ~ 5% Percentage) is best. Here, Lingzhi, Figures 7 (a) and (b), explain the relationship between the amount of pigment added and the color development performance in detail. Fig. 7 (a) shows the relationship between the pigment pigment 10 of the lightweight clay of the present invention, the Christmas ball 12, and the external light 14, 16 in a pattern 4 :. It shows the relationship between the pigment 10, the organic hollow microspheres ", and the external light rays 24 and 26 when the light-weight clay of the present invention makes the pigment used excessively, as shown in Fig. 7 (a). In terms of the added amount, even the surroundings are only partially obstructed. As for the lightweight dot pigment pigment 10 of the present invention, it is attached to a degree of covering, so the hollow microspheres 2 of the pigment pigment 10 in the outer soil The amount of light that can be added to the light rays 1 4 and 16 is more than the circumference of the predetermined microsphere 22. In Fig. 7 (b), because the pigment pigment 10 has a larger value, the pigment pigment 10 adheres to the organic matter. 5.593.21 V. Description of the invention (24) There are sometimes double-layer attachments, so it will cause a situation that prevents the external light 24, 26 from passing through. Therefore, in the lightweight clay of the present invention, it is satisfactory that The combination of specific organic hollow microspheres 12 and pigments containing pigments 10 can effectively prevent the scattering of light from organic hollows and spheres 12 to obtain bright and transparent color development performance. (5) Water-dispersible pigments are water-dispersible (including Alcohol dispersibility), that is, hydrophilic is better. The reason is that by using a pigment with this characteristic, even if the amount of clay contains water or alcohol, the pigment will not coagulate. Color performance and styling performance. In addition, if the pigment is water-dispersible, it can be stored in water even if the pigment is fine particles, and it can also be stored in the state of this solution. Deployment.

In order to make the pigment water-dispersible, it is preferred that the resin constituting the pigment has a value in the range of p 300 to 300. Ren Fan A The reason is that, when the resin acid value is less than 50, the dispersion of the winter water obtained by the household pi will be significantly reduced; on the other hand, when the resin At 300, the obtained pigment is liable to coagulate. Therefore, in order to achieve a good balance between the above-mentioned value and the dispersibility and coagulability of the prime water, the color of the tree that constitutes the pigment is more preferably in the range of 70 ~ 250, with a shovel of 90 ~ 200: 5 hours The value is best. The calculated value is within the range. In addition, in order to control the acid value of the resin constituting the pigment, the range should include carboxyl, sulfonic acid, and hydroxyl groups in the molecule.

_ I 闘 P.27 593201 V. Invention Explanation * 25. That is, it is preferable to use a styrene maleic acid copolymer resin, a styrene sulfonic acid copolymer resin, a styrene-acrylic acid copolymer resin, or the like. In order to make the pigment water-dispersible, the form is preferably an emulsion containing a surfactant such as an anionic surfactant or a cationic surfactant. As such a surfactant, one or a combination of two or more of the following exemplified ethyl compounds may be sodium dodecylbenzenesulfonate, sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate Ammonium salts, polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkylamines, polyoxyethylene alkylamines. Gas 6 · Fluorescent whitening agent (1) As a fluorescent whitening agent added to lightweight clay, it can be a 1,2-stilbene compound, a 1,2-stilbene inducer, or 1,2 -Dibenzyl ethylenesulfonic acid compounds, thiophene compounds, thiophene inducers, and the like. In particular, the 1,2-stilbene sulfonic acid compounds shown in the following formulae (1) to (3) are each anionic water-soluble and have the advantage of being easy to use. If they are added in small amounts, You will get excellent fluorescent whitening effect.

S0JW

CH = CH ⑴

Page 28 593201 V. Description of the invention (26) [In the formula (1), the symbol M is hydrogen, an alkaline metal, or any cation represented by ammonium and amine ions, and X and Υ are independent substituents. That is, an arbitrary substitution group represented by NH2, N (C2IUOH), N (CH 乂 CH (0H) CH3) α, or nr'rW and a hydrocarbon group having 1 to 20 carbon atoms or hydrogen). ]

CH = CH

⑵ [In the formula (2), the symbols X and Y are independent substituents, that is, SOj (the symbol M is hydrogen, an alkaline metal, or any cation represented by ammonium and amine ions), NΗ, N (CzH40H) z KCHiCIUOiOCHa) ζ, or nVr ^ R / and R2 · is a hydrogen or a hydrocarbon group having 1 to 20 carbon atoms)). ]

SOM

SO, Μ CH = CH

⑶

Page 29593201 V. Description of the invention (27). [In the formula (3), the symbol X is NHz, N (C2m〇H) z, N (CHaCH (0H) CH >) ζ, or NR / r ^ R / and Y are arbitrary substituents represented by hydrogen or a hydrocarbon group having 1 to 2 carbon atoms. ] (2) Density The density of the fluorescent whitening agent is preferably within a range of 0.9 to 2. Og / cm3 (measurement temperature: 20 ° C, the same below). The reason is that when the density of the fluorescent whitening agent is outside this range, it becomes difficult to uniformly mix the light-weight clay. Therefore, the density of the fluorescent whitening agent is more preferably in the range of 1.0 to 1.6 g / cm3, and most preferably in the range of 1.1 to 1.4 g / cn ^. (3) Viscosity The viscosity of the fluorescent whitening agent is preferably within a range of 5 to 100 mPa · s (measurement temperature: / 2 0 C, the same below). 々 The reason is that when the viscosity of the fluorescent whitening agent is less than 5 mPa · s, it is difficult to uniformly mix in a lightweight clay. On the other hand, when the viscosity of the fluorescent whitening agent exceeds a value of 1000 mPa · s, it not only solidifies and makes the operation difficult, but also makes it difficult to mix uniformly in lightweight clay. Therefore, the viscosity of the fluorescent whitening agent is more preferably within a range of 10 to 500 mPa · s, and most preferably within a range of 30 to 2000 mPa · s.

(4) PH The pH value of the fluorescent whitening agent is preferably within a range of · 1 ~. The reason is that when the p H value of the fluorescent whitening agent is less than 7.1, the light-weight clay is excessively gelled, and its storage stability is lacking. On the other hand, when the pH value of the fluorescent whitening agent exceeds 10, it will cause difficulties.

P.30 593201 V. Description of the invention (28) ′ The problem of using operation. Therefore, the P P value of the fluorescent whitening agent is more preferably in a range of 7.5 to 9 · 5, and most preferably in a range of 8 to 9. (5) Addition π amount The addition amount of the fluorescent whitening agent is preferably within a range of 0.001 to 5% (weight percentage) relative to the total weight. The reason is that when the added amount of the said fluorescent whitening agent is less than 0.01% by weight, the added effect cannot be exhibited, and it is difficult to adjust the L value of lightweight clay. On the other hand, when the added amount of the fluorescent whitening agent exceeds 5% by weight, the L value of the lightweight clay will be saturated, and at the same time, the fluorescent whitening agent will ooze outward. Therefore, the addition amount of the fluorescent whitening agent is relative to the total weight. In other words, it is more preferably in the range of 0. 1 to 3% (weight percentage), so as to be in the range of 0. 0 5 to 1% (weight Percentage) is best. _ In addition, the amount of fluorescent whitening agent should be determined based on organic hollow microspheres. That is, when the added amount of the hollow microspheres is F 1 and the added amount of the fluorescent whitening agent is F 2, the value of F 1 / F 2 is preferably in the range of 1 to 100. The reason is that when the value of F 1 / F 2 is less than 1, the L value of the lightweight clay is saturated, and at the same time, it is difficult to ensure the lightweight of the lightweight clay. On the other hand, when the value of F 1 / F 2 exceeds 100, it is difficult to adjust the L value of the lightweight clay. Therefore, the value of F 1 / F 2 is more preferably in the range of 2 to 50, and more preferably in the range of 5 to 30.

Page 31 593201 V. Description of the invention (29) ‘7 • Gelling agent (1) Type For the main agent such as polyvinyl alcohol, it is suitable to add a gelling agent. In addition, by adding a gelling agent, the handling performance or molding performance of lightweight clay can be significantly improved. Such a gelling agent may be one or a combination of two or more of each of the following agents: osmic acid, borax, Congo red, thizole, catechol, garcinol, gallic acid, and chromic acid (trivalent ), Dichromic acid, acid, vanadate, etc. Among them, boric acid and borax are relatively good gelling agents because they can easily control the gelation of polyvinyl alcohol. (2) Addition amount The addition amount of the gelling agent should be determined in consideration of the handling performance and molding performance of lightweight clay. For example, relative to 100 weight units of polyvinyl alcohol, the added amount is preferably within a range of 0.01 to 10 weight units. ^ The reason is that when the added amount of the gelling agent is less than 0.01 weight unit, the added effect cannot be exhibited. On the other hand, when the amount of the gelling agent added exceeds 10 weight units, it becomes difficult to control gelation of polyvinyl alcohol, which is a lightweight clay. Therefore, the added amount of the gelling agent is more preferably in the range of 0.05 to 5 weight units relative to 100 weight units of polyvinyl alcohol, and in the range of 0.1 to 1 weight units. Within the value is the best. 8 · Filler (1) Type In light clay, it is suitable to add organic filler or inorganic filler. Reason

Page 32 593201 V. Description of the invention (30) * · By adding such a filler, a lightweight clay with superior modeling performance or lightness, or better whiteness can be obtained. This filler can be polymethyl methacrylate, polyethyl acrylate, polystyrene, stupid ethylene propylene copolymer, stupid ethylene vinyl acetate copolymer, polyvinyl acetate, ethylene vinyl acetate copolymer , Polyethylene, ethylene acrylic copolymer, polypropylene, polyvinylidene chloride, vinylidene chloride (vinyl chloride) vinyl acetate copolymer, aldehyde resin, melamine resin, urea resin, Calcium carbonate, talc, oxidized i 仫, silica, mica, pound, oxidized oxide, oxidized complex, oxidized kick, oxidized oxide, indium oxide, carbon, glass, aromatic polyamine fiber, etc.

In particular, talc is cheap and has a good average particle size, so it is easy to use. It is a good filler for adjusting the modeling or lightweight performance of lightweight clay. I (2) Adding amount Ί When adding the filler, the overall weight unit of the lightweight clay is set to 100%, and the adding amount is suitably within the range of 0.1 to 20% by weight. The reason is that when the added amount of the filler is less than 0.1% (weight percentage), the effect of addition cannot be exhibited. On the other hand, when the amount of the filler is more than 20% by weight, the modeling performance and lightness of lightweight clay will be reduced. Therefore, the amount of the filler (when the overall weight unit of the lightweight clay is set to 100%) is more preferably in the range of 0.5 to 15% (weight percentage), to 1 to 10% (weight Percentage) is best.

Page 33 593201 V. Description of the invention (31) · 9 · Whiteness (1) Whiteness What should be the whiteness (WL) of lightweight clay measured according to J IS L 0 8 0 3? Values above 50. The reason is that when the whiteness (W L) of the lightweight clay is less than 50, it will affect its appearance and appearance, and if pigment is added, turbidity will occur, thereby significantly reducing its color development performance. However, when the value of the whiteness (WL) of the lightweight clay is too high, the types of constituent materials that can be used are excessively restricted. Therefore, the whiteness (WL) of the organic hollow microspheres is preferably in the range of 70 to 99.9, and more preferably in the range of 80 to 99. Here, refer to FIGS. 4 and 5 The characteristic graph shown illustrates the relationship between the light weight clay > spoon whiteness (WL) and the evaluation results of the color development performance. In Fig. 4, the white axis (W L) of the lightweight clay is shown on the $ axis, and the evaluation result (relative value) of the color development performance is shown on the vertical axis. In addition, the characteristic curve of the black circle (·) is when the blue pigment is added to 0.22% (weight percent), and the characteristic curve of the black triangle (▲) is added to 0. 1% (weight percent). Of yellow pigment. Moreover, the evaluation result (relative value) of the color development performance is shown in Example 1. The evaluation of ◎ is 5, the evaluation of 4 is 4, the evaluation of △ is 2, and the evaluation of X is 1. The rating is 0. As shown in FIG. 4, for each clay to which a blue pigment and a yellow pigment are added, the higher the whiteness (WL), the higher the evaluation score of the color development performance, especially when the value of the whiteness (WL) is 50 or more. , You can get a high evaluation score.

P.34 593201 V. Description of the invention (32) The amount of fluorescent whitening agent (% (weight percent = ratio)) shown on the y-axis in FIG. 5 is shown in the figure. (Weight percentage) I chromatin, the evaluation result (relative value) of its color development performance. In addition, the black circle (Lu) means light! When the value of whiteness (WL) of the clay is 50 or more (wL-60), the black triangle (▲) indicates a case where the value of whiteness (wl) of the lightweight clay is less than Y0 (WL-0). Therefore, when the value of the whiteness (company) of the lightweight clay is M or more, an evaluation score of 3 or more can be obtained by adding a fluorescent whitening agent of 0. 5 to 0 · 1 ° 彳 (weight percent). In contrast, when the value of the whiteness (WL) of the lightweight clay is less than 50, even if a large amount of fluorescent whitening agent of 0.3 to 0.5% (weight percent) is added, the evaluation point is only at 1 or less. Therefore, it can be understood that if the whiteness (WL) value of the lightweight clay is 50 or more, even if a small amount of fluorescent whitening agent is added, good color development performance can be obtained. i (2) whiteness (WB), whiteness (WL), visual brightness (l value) 4 / whiteness index similar to whiteness (WL) measured in accordance with JISL 0 8 0 3, and also based on blue The whiteness (WB) of the reflectance, the whiteness (WH) according to the Hunter method, and the visual brightness (L value). These whiteness values are the same as those of whiteness (WL) based on JIS L 0803, and are values measured independently. When the whiteness of the lightweight clay is expressed by these whitenesses, for example, the whiteness (W β) based on the blue reflectance is preferably in the range of 60 to 95, and the whiteness based on the Hunter method is similar. The degree (WH) is preferably within a range of 70 to 98, and the visual acuity (L value) is preferably within a range of 80 to 99.

P.35 593201 V. Description of the invention (33) 'I 0 · Other additives In lightweight clay, as additives, in addition to the above-mentioned additives, one or two or more of the following agents can be added as a precautionary measure. Mold agents, antibacterial agents, antioxidants, ultraviolet absorbers, oils, waxes, glycerol, tackifiers, plasticizers, surfactants, organic solvents, etc. II · Manufacturing method (1) Two-pass mixing This process is a process of uniformly mixing the formula materials of organic hollow microspheres, pigments, polar compounds, fibers, and water. For example, in order to uniformly mix and disperse these ingredients, it is preferable to use a propeller mixer, a kneader, a planetary mixer, three rolls, a ball mill, and the like. In particular, since the organic hollow microspheres are light in weight, and are easily destroyed during the kneading process, and the phenomenon of uneven dispersion 4 is also easy to occur, it is preferable to use a kneader. This kneader is preferably extruded and kneaded under the conditions of a rotation speed of 10 to each / 1, 000 rpm and a time of 1 to 60 minutes. It is more preferable to perform extrusion kneading at a speed of 30 to 300 rpm and a time of 10 to 30 minutes. In addition, in order to uniformly mix and disperse the pigment, it should be dispersed in water or alcohol beforehand to adjust into a solution. At the same time, in order to prevent the solution from condensing, it is appropriate to add an alkaline agent and adjust the pH value to 7 or more; It is more preferable to be able to adjust the value within the range of 8 to 10, and the value within the range of 8. 5 to 10 is the best. When mixing formula ingredients, the temperature should be maintained within the range of 30 ~ 70 ° C

P.36 593201 V. Description of Invention (34) · Better. The reason is that when the mixing temperature is less than 30 ° C, the formula materials cannot be uniformly mixed; on the other hand, when the mixing temperature exceeds 70 ° C, the obtained lightweight clay will lose stretch. Sexual and brittle. Therefore, it is better to maintain the mixing temperature in the range of 3 to 60 ° C when mixing the ingredients of the formula, and it is best to maintain the range of 40 to 5 5 ° C. (2) Viscosity adjustment project This project is a process to adjust the viscosity of lightweight clay. In this project, it is suitable to add water, alcohol, or organic solvents, so that the viscosity of the lightweight clay is in the range of 1 X 1 0 3 to 1 X 1 0 9 mPa · s (the measurement temperature is 2 5 ° C, the same below) Within value is better. The reason is that when the viscosity of the lightweight clay is less than 1 X 1 0 3 mPa · s, it will increase the viscosity of the surface and reduce the operating performance; on the other hand, when the viscosity of the lightweight clay exceeds lx At 109 mPa · s, the lightweight clay will lose its stretchability and become brittle, which will also reduce its operating performance. Therefore, the viscosity of the lightweight clay is between 1 X 1 0 4 to 1 X 1 0 8 m P a · The range of s is more preferable, and the range of 1 x 105 to 1 x 107 mPa · s is the best. (3) Packaging Engineering It is best to add a packaging process. This process is a process of packaging the produced lightweight clay in small units. That is, because lightweight clay contains a relatively large amount of water or alcohol, etc., in order to maintain the moisture content and handling performance of lightweight clay, it is suitable to use moisture-proof materials, that is, plastic materials such as polyethylene and polypropylene for packaging.

P.37 593201 V. Description of the invention (35) However, in order to reduce the expansion problem of the unfoamed organic hollow microspheres due to air leakage, a vent hole is provided in the packaging material, or a packaging capable of gas permeation is used. material. At this time, in order to ensure the maintenance of the moisture content of the lightweight clay and reduce the expansion problem, the size of the aeration air is preferably set within a range of 0. 0 1 ~ 1 0 0 # m to set at 0. 0 5 ~ A value in the range of 5 0/2 m is more preferable, and a value in the range of 0.1 to 2 0 " m is the best q. Embodiments Hereinafter, specific embodiments of the present invention will be described in detail. However, the following description is only a good example of the present invention and does not limit the claims of the present invention. [Example 1] (1) Production of lightweight clay In a kneader having a capacity of 100 liters, the following formulation materials were placed, and then rotated at a number of revolutions of 40 r P m to produce clay. White organic hollow microspheres 0.35kg. (Average particle size 1 0 0 // m, whiteness (WL) value is more than 50, weakly alkaline) (weight percentage 2.5%) yellow pigment pigment (solid ) 0 · 10kg (average particle size 0 · 0 86 // m, standard deviation 0 · 0 2 6 / 2m, 95% range 83 — 90 // m) (weight percentage 0 · 7%) carboxymethyl cellulose 0 35kg (degree of etherification 0 · 6) (weight percentage 2.5%)

Page 38 593201 V. Description of the invention (36) 1.05kg

PVA (copolymerization degree 1,800, saponification degree 95mol%) (weight percentage 7.5%) 0. 98kg broadleaf pulp (average fiber length 1 mm) (weight percentage 7.0%) 11.14kg water (weight percentage 79. 6 %) Phenol-based preservative 0.03kg (weight percentage 0.2%) In addition, after mixing the formulation materials uniformly, 8% (weight percentage) of talc (density 2.82g / cm3) as the lightweight clay of Example 1. However, when measuring the whiteness of lightweight clay using a colorimeter TC-18 0MK2 (manufactured by Tokyo Denshokusha Co., Ltd.), the yellow pigment must be removed from the above formula. (2) Evaluation of lightweight clay The obtained lightweight clay was evaluated for its modeling properties (film-forming properties), lightweight properties, color development properties, stickiness, and swelling properties (storage properties). The obtained results (average evaluation of the number of n = 5) are shown in Table 1. Modeling performance The modelling performance (film-forming performance) of lightweight clay is evaluated according to the following criteria. And if you get an evaluation of 0 or more, it can be said to have appropriate

Page 39 593201 V. Description of the invention (37) ′ For the modeling performance of lightweight clay. ◎ The film can be formed into a film with a thickness of 0.2 mm or less using a roll. 〇The roll can be used to form a film with a thickness of 1 mm or less. △ Films with a thickness of 5 mm or less can be formed using a roll. X Even when using a roll, it is not possible to form a thin film with a thickness of 5 mm or less. Lightweight performance The lightweight performance of lightweight clay is evaluated based on the following criteria. In addition, if the evaluation is 0 or more, it can be said that the lightweight clay has sufficient lightweight performance.为 is a value with a density of 0.3 g / cn ^ or less. 〇 is a value with a density of 0.5 g / cm3 or less. Δ is a value with a density of 0.7 g / cm3 or less. X is a value whose density exceeds 0.7 g / cm3. Color development performance Light weight clay development performance was evaluated according to the following criteria. In addition, if the above evaluation is obtained, it can be said that the color development of this lightweight clay is good. ◎ A clear color with a sense of transparency. 〇 is bright colors. △ is a slightly bright color. X is not a vivid color. X X is a turbid color different from the color of the added pigment. Stickiness The stickiness of lightweight clay is evaluated by the following criteria by touching it with a finger 1

II

III Page 40 593201 V. Description of Invention (38) " _______. In addition, if '0' or higher is obtained, the soil has good viscosity. ° 子 彳 贝 'can be said to be light-weight sticky ◎ Almost not sticky. 〇Slightly sticky. △ Sun is obviously sticky, but the light clay is not. X is obviously sticky, and the light clay is sticking. Swelling performance 隹 on your fingers. 100 g of lightweight clay was molded into long / film wraps around it. And in this state, the shape can be reduced, and the volume is measured after the thin layer of polyethylene with a thickness of 100. According to the initial capacity == 1 star price expansion performance placed in the box (storability f M. ^ The relationship between the product and the following benchmark evaluation Can this lightweight clay? Second, if it obtains an evaluation of 0 or more, 'the volume change rate is less than 3% " τ and, & swellability (storage performance). The volume change rate is less than 10%. The volume change rate is less than 3 〇%., X volume change rate exceeds 30% or more.

The weather resistance k π Μ 廿 A f of the lightweight clay is evaluated based on the following criteria. If the above evaluation is obtained, it can be said that it has weather resistance suitable for lightweight clay. ◎ It does not change color even when it is irradiated with ultraviolet light of 100 mJ / cn ^. 〇Almost does not change color even when irradiated with 5000 m J / cm. △ When it is irradiated with ultraviolet light of 50 m J / crn ^, there is little discoloration. When X is irradiated with 500 m J / cnT ultraviolet rays, there is obvious discoloration. Fading resistance 593201

V. Explanation of the invention (39) If the color fading of the pigment in the lightweight clay is evaluated as 0 or more, it can be said that the evaluation is based on two benchmarks. Such as the amount of fade resistance of clay. ’, Pigments are suitable for light pigments Pigments do not adhere ◎ Even light clay and pinch for 5 minutes with your hands. 〇Even if light clay and pin 5 are attached to the hand. △ Put the lightweight clay by hand and pinch for 5 minutes on the hand. X will light $ clay by hand and pinch for 5 minutes. Dividing, the pigment is almost not, the pigment is slightly attached, and the pigment is obviously attached to the hands [Examples 2 to 4, and Comparative Examples 1 to 3] As shown in Table 1, there are six changes and In Comparative Examples 1 to 3, each of the four labors used for tillering: the type of the pellet (outside the implementation m) and the value of l were insufficient. Make 'average particle size of 10 ~, white shame average diameter, Tim! 4 = / acid brown color has a shot of the minute beauty in the same way as in Example i ;; said the amount of H fiber or water added to: Implementation The same method is used in Example i; at first, the light clay obtained by Γ can be used as a result of Λ: Λ. The results are shown in Table 1. Amount of more than 5%

Performance, or expansive knife :: ’The modeling performance of lightweight clay and the evaluation of sexual behavior will be significantly reduced. (Ratio) τ and: the amount of the added material is less than 10% (weight percent. U is different ’can also be sought for lightweight clay)

593201 V. Description of the invention (40) Light weight of points. In addition, unlike the conventional viewpoint, even if the amount of water added exceeds 60% by weight, the viscosity of the lightweight clay can be sufficiently adjusted to a suitable value. Table 1 Examples Examples Examples Examples Proportions Proportions Proportions 1 2 3 4 1 2 3 Adhesive resin PVA / CM PVA / CM PVA / CM PVA / CM PVA / CM PVA / CM PVA / CM Addition ratio CCCCCCC Addition amount ( % 100/33 100/33 100/33 100/33 100/33 100/33 100/33 100/33 (weight percentage) 10 10 10 10 10 10 10 Organic hollow microspheres 100 100 110 40 40 40 40 Average particle size 2.5 2.0 2.9 4.0 7.0 10 88 88 88 78 78 78 1 View (# ΠΊ) Addition (% (weight percent)) Whiteness (WL) (% (weight 7 7 7 7 25 20 15 volume percent)) Water (% (weight (Percent)) 79.6 80.1 79.2 78.1 57.1 59.1 59.1 Pigment (% (weight 0.7 0.7 0.7 0.7 0.7 0.7 0.7 volume percentage))

Page 43 593201 V. Description of the invention (41) Characteristic evaluation Whiteness (WL) Shaping performance Lightweight performance Discoloration performance Viscosity expansion performance Weathering performance Fade performance ^ @ 0 © @ © 0® ^ Asx @ xx © ^ x @ x © xx © ^ x © x © xx © [Examples 5 to 8, and Comparative Examples 1 to 3] As shown in Table 1, with respect to the total weight (100% (weight percent)), Whitening agent (anionic 1,2 stilbene sulfonic acid compound, properties: liquid, density: 1.2 2 g / c m5, P Η value: 8 to 9, viscosity: 30 to 50 mPa · s (measurement temperature : 20 ° C)) The light weight clay was produced in the same manner as in Example 1 except that the formula ratio with PVA was changed. Next, the obtained lightweight clay was evaluated in the same manner as in Example 1. The results are shown in Table 2. From the results, it can be easily understood that by adding a certain amount of fluorescent whitening agent, the whiteness (WL) of the obtained lightweight clay can be easily adjusted to a value of 50 or more, and the weather resistance can be significantly improved. And hair color performance. Therefore, even if the formed lightweight clay is left by a window for a long time and irradiated with sunlight, excellent color development performance can be maintained.

Chapter 59591

P.45 593201 V. Description of the invention (43) 'Industrial use of the lightweight clay of the present invention' Since the diameter of the organic hollow microspheres is in the range of 15 ~ 150, the addition amount is 0 ·] ~ 6 / denier Grain fraction ratio) (with respect to the total weight, t) · '^ two hundred hundred ji SL 0 8 0 3 as a reference for the measurement of the light weight of clay, the "color value (WL)" is above; therefore Light 1 clay has superior hair color, and sex; and when covered with packaging materials; type! = Light ^ When the ambient temperature rises to a high temperature, etc., the combination of two: two :, the problem, has a good storage performance; at the same time, it has two lambda expansion = T L and has the advantage of low production costs. m: In addition, 'in the lightweight clay of the present invention, by setting the formula ratio of CMC and PVA within a range of 1 0. 4 0 to 10 0: 5 0 0, it is easy to shape a predetermined shape. At the same time, it also realizes the difficult film thinning (such as thin film thickness less than 0.1 mm) in the prior art, and is also suitable for decorative materials or origami. The light weight clay of the present invention is excellent because it is added with a quantitative pigment having a flat surface diameter of 0. 0 5 to 0, 2 / zm and a standard deviation of the particle size distribution of 0. 05 am. At the same time as the color development performance, it also has excellent light resistance and color fastness. In the manufacturing method of the lightweight clay of the present invention, since organic hollow microspheres having an average particle diameter in the range of 15 to 150 // m are used and kneaded by a kneader, and the amount of organic hollow microspheres added The whiteness (WL) of the lightweight clay measured in accordance with JISL 0 8 03 is within the range of 0.5 to 6% (weight percentage) (relative to the total weight).

Page 593201

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593201 Brief description of the drawings ’[Illustration of the drawings] Figure 1 shows the relationship between the amount of organic hollow microspheres in lightweight clay and the lightweight performance and modeling performance of lightweight clay. Fig. 2 is a characteristic diagram showing the relationship between the amount of organic hollow microspheres added in lightweight clay and the results of evaluation of swelling performance. Figure 3 is a graph showing the relationship between the amount of organic hollow microspheres added in lightweight clay and the cost ratio. Figure 4 is a graph showing the relationship between the whiteness (WL) of light-weight clay and its color development performance. Fig. 5 is a characteristic diagram showing the relationship between the amount of fluorescent whitening agent added and the color development performance of lightweight clay. Fig. 6 (a) is a graph showing the relationship between the average particle size of the pigment material in the lightweight clay of the present invention and the light transmittance (color development property).

Fig. 6 (b) is a graph showing the relationship between the average particle size of the pigment material in the conventional light-weight clay and the light transmittance (color development property). Fig. 7 (a) is a graph showing the relationship between the amount of the pigment material in the lightweight clay of the present invention and the light transmittance (color development property). Figure (b) shows the relationship between the amount of pigment material added and light transmittance (color development performance) in the conventional lightweight clay. [Illustration of drawing number] 1 2 Organic hollow microspheres 16 External light 2 2 Organic hollow microspheres 26 External light 1 0 Pigment pigment 14 External light 20 Pigment pigment 2 4 External light

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Claims (1)

593201 —Revised core .. 矣 Big riddle 91911324 January 1, a lightweight clay containing organic hollow microspheres and a binder resin, characterized in that the average particle size of the organic hollow microspheres is set to 2 In the range of ~ 150 smoke, the addition of the organic hollow microspheres is set within a range of 6% (weight percent) or less relative to the total weight; and measured in accordance with JIS L 080 3 The whiteness (WL) value of the light-weight clay was 50 or more. ^ The lightweight clay as described in Item 1 of the declared patent scope, characterized in that the value of the whiteness (WL) measured by the organic hollow microspheres according to j 丨 S L 〇 0 0 3 is 50 or more. 3. The lightweight clay according to item 1 of the scope of the patent application, characterized in that it also contains a fluorescent whitening agent, and the added amount of the fluorescent whitening agent is relative to the total weight. Within the range of 0.001 to 5% (weight percent). 4. The light clay as described in item 3 of the scope of patent application, characterized in that the surface of the organic hollow microspheres is surface-treated with the fluorescent whitening agent. 5. The lightweight clay according to item 3 of the scope of patent application, characterized in that the added amount of the organic hollow microspheres is set to F 1, and the added amount of the fluorescent whitening agent is set to At this time, the value of F1 / F2 is in the range of 1 ~ 100. 593201 —---- Case No. 91119324 6. Scope of patent application 3, Lightweight clay as described in item 1 of the scope of patent application, characterized in that when the density of other constituent materials except the organic hollow microspheres is 5 Q 5 ~ Insufficient (in the case of K8g / cm2, the added amount of the organic hollow microspheres is within the range of 0.1% to less than 3% by weight relative to the total weight; when the organic hollow is excluded When the density of constituent materials other than the microspheres is 0.8 to 5 g / cm2, the amount of the organic hollow microspheres added is in the range of 0.1 to 6% by weight based on the total weight. 7 ~. The lightweight clay as described in item 1 of the patent application scope, characterized in that the binder resin is a hydroxyl-containing compound and a carboxyl-containing compound, or a polar compound containing either of them; The polar compound is ^ relative to the weight of the f-body, and its added amount is in the range of 0.1 to 3% by weight (weight percentage). 8. The first scope of the application for a patent lies in the hydroxyl-containing compound vitamins and Polyvinyl alcohol; and And, the lightweight clay according to 3, 7 or 7, its characteristics and carboxyl-containing compounds, including carboxymethyl cellulose The formula ratio (where ^ = Μ does not contain the above-mentioned fluorescein polyvinyl alcohol) is within the range of carboxymethyl cellulose and; the star ratio is 100: 40 ~ 100: 500 The said carboxymethylcellulose and poly p.593201 ---- case number 91119324_ ^ a_amendment_ Sixth, the scope of patent application (the weight ratio) of vinyl alcohol is in the range of 100: 55. 100: 2, 000. 9. The lightweight clay according to item 1 of the scope of patent application, characterized in that the lightweight clay further contains fibers, and the amount of the fiber added is 1% to the total weight. Within the range of less than 10% by weight. 10. The lightweight clay according to item 1 of the scope of the patent application, characterized in that the lightweight clay further contains water, and the amount of water added is 61 to the total weight. Within the range of ~ 85% (weight percent). 11. The lightweight clay according to item 1 of the scope of the patent application, characterized in that the lightweight clay further contains a pigment, and the added amount of the pigment is 0 to the total weight. The value ranges from 0 1% to less than 10% by weight. 1 2. The lightweight clay according to item 丨 丨 in the scope of patent application, characterized in that the average particle diameter of the pigment is in the range of 0.05 to 0.2, and the standard deviation of the particle size distribution is 〇5 〇 The value below ⑺. 1 3. The lightweight clay according to item 丨 丨 or 12 of the scope of patent application, characterized in that the average particle size of the pigment is set to D1, and the organic hollow Page 51 593201 --- ^ Mm 91119324 Λ-3.-a_M ___ VI. Patent Application Range The average particle size of the microspheres is set to D2. At this time, the ratio of D2 / D1 is in the range of 10 ~ 50,000. 14. The lightweight clay according to item 1 of the scope of the patent application, characterized in that the lightweight clay further contains a filler, and that the amount of the filler is relative to the total weight. · Within the range of 1% to less than 20% by weight. 15. The lightweight clay according to item 1 of the scope of patent application, characterized in that the lightweight clay also contains inorganic hollow microspheres, and the inorganic hollow microspheres are relative to the total weight The added amount is in the range of 0.001 to 10% by weight. 16 kinds of manufacturing methods of wheeled clay, which are manufacturing methods of lightweight clay containing organic hollow microspheres and a binder resin, are characterized in that the average particle diameter of the organic hollow microspheres is 15 to 15 In the range of 0 ', the added amount is a value below 6% (percent by weight) (relative to the total weight); At the same time, the organic hollow microspheres and the binder resin are kneaded with a kneader, so that according to jIS The value of whiteness (WL) of the lightweight clay measured at L 08 0 3 is 50 or more. Page 52