JP2019006015A - Straw containing molding and production method for straw containing molding - Google Patents

Abstract

To provide a straw containing molding being excellent in mechanical strength and also excellent in surface smoothness and the like even with a relatively low content of binder resin and an efficient production method therefor.SOLUTION: Provided are a straw containing molding obtained by forming a straw containing composition containing (A) straw, (B) an isocyanate-based adhesive and (C) water into a specified shape by heating molding, and its production method, characterized in that with respect to 100 pts.wt. of (A) the straw, a content of (B) the isocyanate-based adhesive is in a range of 10-50 pts.wt., and the (A) straw has an average length in a range of 50-150 mm and (A) the straw is orientated in horizontal direction along the surface direction.SELECTED DRAWING: Figure 1

Description

The present invention relates to a wrinkle-containing molded article and a method for producing a wrinkle-containing molded article.
In particular, a cocoon-containing molded product obtained by reusing agricultural waste, which is lightweight (low density) and has excellent mechanical strength, etc., and such cocoon-containing molded product The present invention relates to an efficient manufacturing method.

In recent years, straw as an agricultural waste (rice straw and wheat straw, hereinafter the same) has been produced in large quantities with the production of rice wheat, and their disposal and reuse methods have become a problem.
Therefore, studies have been made to effectively utilize the light weight and low cost of straw as agricultural waste as part of building materials.

For example, to make effective use of agricultural waste and to provide a hot-press molded board with excellent mechanical strength, wheat straw pieces and / or rice straw pieces, kenaf chips, and organic polyisocyanate as an adhesive A method for producing a hot-press molded board using a compound has been proposed (for example, see Patent Document 1).
More specifically, in the examples, for example, 500 g of wheat straw cut to a length of 1 to 3 cm with a cutting machine, 300 to 500 g of chips crushed kenaf, and water dispersion of an organic polyisocyanate compound as an adhesive 130 g of liquid (solid content: 77%) was placed in a blender and formed, and then heated and compressed with a press machine having a surface temperature of 180 ° C., density 0.7 g / cm ³ , thickness 10 mm, bending strength 20.1 A hot press molded board of ˜37.5 MPa was obtained.
On the other hand, in a comparative example, without using a chip obtained by pulverizing kenaf or the like, 500 g of wheat straw or rice straw cut into a length of 1 to 3 cm with a cutting machine, and 130 g of an aqueous dispersion of an organic polyisocyanate compound as an adhesive, Is formed in a blender and then heated and compressed with a press machine having a surface temperature of 180 ° C., a hot-press molded board having a density of 0.7 g / cm ³ , a thickness of 10 mm, and a bending strength of 16.4 to 18.7 MPa is obtained. It was.

In addition, in order to reduce the amount of wood used and to supply it cheaply and stably, a core board made by hardening wheat straw pieces and / or rice straw pieces with a binder and a finishing material using the same are proposed. (For example, refer to Patent Documents 2 and 3).
More specifically, as shown in FIG. 10, a mixture containing wheat straw pieces and / or rice straw pieces 102, wood chips or wood fibers 103, and diphenylmethane isocyanate or a phenol formaldehyde compound as a binder 104. This is a core board 101 obtained by thermosetting and the like.
Then, a semi-cured prepreg sheet is separately prepared and laminated on the surface of the core board 101, and further, a heat-pressing process is performed through the prepreg sheet, thereby applying a decorative material (not shown). It is a laminated finish.

JP 2003-31720 A (Claims etc.) JP 2002-36213 A (Claims etc.) JP 2002-36214 A (Claims etc.)

However, in Patent Document 1, in the production of a hot-press molded board, a chip obtained by pulverizing kenaf other than wheat straw pieces and / or rice straw pieces cut into a predetermined length is essential as a blending component. There was a problem that it was difficult to mix uniformly.
Therefore, there has been a problem that the thickness, bending strength, and the like of the hot-press molded board obtained by heat molding vary greatly.
In addition, chips made by grinding kenaf are indispensable, and there is a risk of parasitic insects when using hot-pressed boards for wooden packing materials. There was a problem that prescribed fumigation treatment had to be performed in accordance with “International Standard for Phytosanitary Measures: ISPM NO.15”.

In addition, the core board disclosed in Patent Document 2 and Patent Document 3 each need a wood-based chip or a wood-based fiber in addition to the wheat straw pieces and the like. There were problems that it was difficult to mix and that it was necessary to perform a predetermined fumigation treatment in accordance with the guidelines of the International Food and Agriculture Organization (FAO).
In addition, in order to construct the finishing material from the core board, it is necessary to laminate a prepreg sheet or a decorative material on the surface of the core board, but the surface smoothness of the obtained core board is poor, There was also a problem that it was difficult to laminate.

Therefore, in view of the circumstances as described above, the present inventors have reused straw having a predetermined length derived from agricultural waste, such as Indica rice, and a relatively small amount of binder resin ( The present invention was completed by finding that a wrinkle-containing molded product having a light weight (low density) and excellent mechanical strength can be efficiently obtained by heat molding using a predetermined adhesive). It has been made.
That is, the object of the present invention is a soot-containing molded product obtained by reusing agricultural waste, which is excellent in light weight and has excellent mechanical strength even when the binder resin is relatively small. Another object of the present invention is to provide an inexpensive soot-containing molded product and an efficient method for producing such a soot-containing molded product.

According to the present invention, there is provided a flat plate-like mold-containing molded product obtained by heat-molding a bag-containing composition containing (A) bag, (B) an isocyanate-based adhesive, and (C) water. ,
(A) For 100 parts by weight of basket
(B) The amount of the isocyanate-based adhesive is set to a value within the range of 10 to 200 parts by weight,
(C) The amount of water is set to a value within the range of 10 to 30 parts by weight,
(A) The average length of the wrinkles is a value within the range of more than 30 mm to 150 mm,
The thickness of the flat plate-like molded product is a value within the range of 3 to 50 mm,
And (A) The cocoon-containing molded product characterized in that the cocoons are arranged in a random direction or a predetermined direction along the surface of the flat cocoon-containing molded product (that is, in the horizontal direction), The problems described above can be solved.
That is, the straw that is agricultural waste is reused to obtain a predetermined length of (A) straw, and (B) an isocyanate-based adhesive and (C) water are blended at a predetermined ratio. When the contained composition is constituted and the wrinkle-containing composition is thermoformed into a flat plate having a predetermined thickness, (A) the whole wrinkle is in a random direction or a predetermined direction along the surface, but in the horizontal direction. Can be uniformly arranged or laminated.
Therefore, it is possible to obtain a wrinkle-containing molded article having excellent mechanical strength and excellent surface smoothness and economy while being lightweight.
In addition, (C) a cellulose mainly having a large number of hydroxyl groups as a main component and uniformly oriented (A) soot and (B) an isocyanate-based adhesive chemically react with each other through water. It is possible to improve the adhesion between the rice straws to be produced, and to make the rice cake-containing molded article further excellent in mechanical strength.
In addition, since it does not contain natural wood or kenaf as a raw material, even if the prescribed fumigation treatment is omitted or the fumigation treatment time is shortened, there is no parasitic inclusion due to pests. Product.

Moreover, when composing the rice bran-containing molded product of the present invention, it is preferable that (A) rice bran is rice bran after harvesting indica rice.
A rice bran derived from Indica rice has a feature that it is relatively long and supple compared to a rice bran derived from japonica rice and the like, so that it is easy to roll in a roll shape.
Therefore, cocoons derived from indica rice can be obtained easily and in large quantities by mechanical and automatic cutting or the like. As a result, when a cocoon-containing molded product is obtained, mechanical strength and surface smoothness are obtained. Furthermore, a more excellent and cheaper soot-containing molded product can be obtained.

Moreover, when composing the soot-containing molded product of the present invention, the density measured in accordance with JIS A 5905 is preferably set to a value of 550 kg / m ³ or less.
By comprising in this way, the density of the obtained soot-containing molded product can be quantitatively managed to ensure the desired light weight, and as a result, a loading platform member that requires predetermined light weight ( It can be used in a wide range of applications, including pallets) and wood replacement applications.

Moreover, when composing the soot-containing molded article of the present invention, the surface hardness measured in accordance with JIS A 5905 is preferably set to a value in the range of 1 to 50 N / mm ² .
By configuring in this way, it is possible to quantitatively manage the surface hardness of the obtained wrinkle-containing molded product to ensure the desired mechanical strength and usability, and thus a predetermined surface hardness is required. It can be used in a wide range of applications including pallet and other wood replacement applications.

Moreover, when comprising the wrinkle containing molded article of this invention, it is preferable to make the bending strength measured based on JISA5905 into the value within the range of 1-100 Mpa.
By constituting in this way, it is possible to quantitatively manage the mechanical strength of the obtained soot-containing molded product to ensure the desired mechanical strength and usability, and as a result, the predetermined bending strength, etc. It can be used in a wide range of applications, including the required parts for loading platforms (pallets) and other uses for wood substitutes.

Moreover, when composing the soot-containing molded article of the present invention, (B) the isocyanate-based adhesive contains butadiene having a hydroxy group as a main agent and an isocyanate compound as a curing agent, and (A) 100 It is preferable to contain (B) isocyanate adhesive in the range of 10 to 200 parts by weight with respect to parts by weight.
Thus, by blending (B) the isocyanate-based adhesive at a predetermined ratio, it is possible to improve the adhesiveness between the ridges mainly composed of cellulose acetate, and as a result, excellent mechanical properties when thermoformed. Since it has strength and surface smoothness, it can be a wrinkle-containing molded product having a decorative layer having a uniform thickness on the surface.

Moreover, when composing the soot-containing molded product of the present invention, it is preferable that the soot-containing composition further contains (D1) a fumigant and (D2) a flame retardant, or one of them.
With this configuration, even if the prescribed fumigation treatment is omitted or shortened according to the guidelines of the International Food and Agriculture Organization (FAO), which is essential for natural timber products, infestation by pests Is further eliminated, and a soot-containing molded product with superior safety and hygiene can be obtained.
Moreover, even if a soot-containing composition contains a flame retardant, the flame retardancy of the soot-containing molded product can be effectively improved even when a relatively small amount of the flame retardant is blended.
Conversely, when the soot-containing molded article of the present invention does not contain a predetermined amount of flame retardant, it has the advantage that it can be incinerated and used as fuel after a certain period of use.

Moreover, another aspect of the present invention provides a plate-like cocoon-containing composition formed by thermoforming a cocoon-containing composition containing (A) cocoon, (B) an isocyanate-based adhesive, and (C) water. A method for producing a molded article, comprising the following steps (1) to (3).
(1) Cutting the raw material cocoons so that the average length becomes a value in the range of more than 30 mm to 150 mm to obtain (A) cocoon having a predetermined length (2) (A) 100 parts by weight of cocoon In contrast, (B) an isocyanate-based adhesive is blended so as to have a value within the range of 10 to 200 parts by weight, and (C) water is blended so as to have a value within the range of 1 to 30 parts by weight. Step (3) Heat-molding the soot-containing composition under conditions of 150 to 180 ° C. and ^{2 to} 100 kgf / cm ² , the thickness is in the range of 3 to 50 mm, and (A) soot is A thermoforming process for forming a wrinkle-containing molded product horizontally oriented in a random direction or a predetermined direction (one direction) along the surface of the flat wrinkle-containing molded product. , Recycle the agricultural wastes to make (A) wastes of a certain length, and ( B) When a cocoon-containing composition formed by blending an isocyanate-based adhesive and (C) water at a predetermined ratio is formed, and the cocoon-containing composition is thermoformed into a flat plate having a predetermined thickness, A) The entire ridge can be uniformly arranged in the horizontal direction or laminated in the random direction or the predetermined direction (one direction) along the surface.
Accordingly, it is possible to stably obtain a wrinkle-containing molded article that is lightweight but has excellent mechanical strength and excellent surface smoothness.
In addition, since the rice bran-containing molded product is formed by heat molding in such a relatively low pressure condition, the occurrence of internal stress in the rice bran-containing molded product is reduced, and the occurrence of warpage and the like over time is effective. It can also be prevented.
Furthermore, natural wood, kenaf and the like are practically not included, and (A) the blending amount of natural wood, kenaf and the like is 10 parts by weight or less, more preferably 0 weight, with respect to 100 parts by weight of firewood. It is possible to prevent adverse effects on dispersibility and high costs due to the blending of wood and kenaf.
In addition, since it is heat-molded at a predetermined temperature, even if the predetermined fumigation treatment is omitted or shortened, it is possible to efficiently obtain a fumig-containing molded product free from infestation by pests.

FIG. 1 is a diagram provided to explain the relationship between the average length of wrinkles and the density of wrinkle-containing molded products. FIG. 2 is a diagram provided for illustrating the relationship between the average length of wrinkles, the surface hardness of wrinkle-containing molded products, and the manufacturing costs. FIG. 3 is a diagram provided for explaining the relationship between the average length of the wrinkles and the bending strength of the wrinkle-containing molded product. FIG. 4 is a diagram showing an appearance (roll shape) formed by sweeping rice cakes derived from indica rice. FIGS. 5A to 5B are views for explaining a planar state of a cocoon-containing molded product using cocoons having different average lengths (the cocoon lengths: more than 30 mm and 50 mm). FIGS. 6A to 6B are views provided to explain the appearance of the soot-containing molded products having different thicknesses (thickness: 19 mm and 30 mm), respectively. FIGS. 7A to 7C are views provided to explain a cross-sectional state of a bag-containing molded product and its application example. FIGS. 8A to 8C are a perspective view, a side view, and a front view when the bag-containing molded product is used for a pallet. 9 (a) to 9 (f) are diagrams provided to explain the heat forming step of the soot-containing molded product. FIG. 10 is a diagram for explaining a conventional bag-containing molded product.

[First Embodiment]
The first embodiment is a flat plate-like mold-containing molded product obtained by heat-molding a bag-containing composition containing (A) a bag, (B) an isocyanate-based adhesive, and (C) water. And
(A) For 100 parts by weight of basket
(B) The amount of the isocyanate-based adhesive is set to a value within the range of 10 to 200 parts by weight,
(C) The amount of water is set to a value within the range of 10 to 30 parts by weight,
(A) The average length of the wrinkles is a value within the range of more than 30 mm to 150 mm,
The thickness of the flat plate-like molded product is a value within the range of 3 to 50 mm,
And (A) A wrinkle-containing molded product characterized in that the wrinkles are horizontally oriented in a random direction or a predetermined direction (one direction) along the surface direction of the flat plate-shaped wrinkle-containing molded product.
The wrinkle-containing molded product of the first embodiment will be specifically described below with reference to the drawings as appropriate. FIGS. 1 to 3 show (A) the average length of wrinkles and various characteristics (density, surface hardness). 4 is a diagram showing the appearance (roll shape) of rice bran derived from Indica rice, and FIG. 5 is a diagram showing the surface state and the like of the rice cake-containing molded product. FIG. 6 is a diagram showing the appearance of the cocoon-containing molded product, FIG. 7 is a diagram showing a cross-sectional state of the cocoon-containing molded product, and FIG. 8 is a diagram showing the cocoon-containing molded product on the pallet. It is a figure which shows the external appearance at the time of using.

1. (A) Component: Koji (1) Type (A) Koji (rice koji) 10a included in the koji-containing molded product 10 of FIGS. 7 (a) to (c) Stems after threshing and stems derived from various grains derived from rice, wheat, straw, etc. can be used.
Accordingly, (A) rice bran 10a is typically rice straw or wheat straw.

In addition, regarding the types of rice that can be harvested with a predetermined length, there are roughly indica rice, japonica rice, and Japana rice. Of these, as shown in FIG. 4, rice after harvesting indica rice is included. More preferably, it is a cocoon.
The reason for this is that cocoons derived from indica rice usually have a length exceeding 1.5 m, and are relatively long and supple compared to short cocoons derived from japonica rice. And it has the feature that it is easy to roll a roll.
Therefore, if the cocoon is derived from Indica rice, as shown in FIG. 4, it is easy to make a long roll, and then a predetermined amount of cocoon can be fed into a thread and cut into a predetermined length. It can be handled very easily.
That is, (A) ridges adjusted to a predetermined length can be obtained easily and in large quantities by mechanical and automatic cutting or the like. Therefore, when a wrinkle-containing molded product is obtained using such a wrinkle, it is possible to obtain a wrinkle-containing molded product that is more excellent in mechanical strength and surface smoothness and is less expensive.
Therefore, rice straw derived from indica rice is not only easy to handle, but also can be obtained easily and in large quantities by cutting or the like. That is, when a rice bran-containing molded product is obtained using such rice straw, a rice bran-containing molded product having further excellent mechanical strength and surface smoothness can be obtained at low cost.

In addition, regarding the types of wheat that can be taken a predetermined length of the barley, broadly classified as barley (including beer barley), wheat, rye, pigeons, and oats, of which barley and wheat are harvested. It is more preferable that it is the wheat straw after.
The reason for this is that such wheat straw has a characteristic that the stem length is relatively long and thick. Therefore, such a wheat straw is not only easy to handle, but also is likely to be horizontally oriented even with a relatively small amount. That is, even when such a wheat bran is used to obtain a koji-containing molded product, a koji-containing molded product having a reasonably good mechanical strength and surface smoothness can be obtained at a low cost.

(2) Average length In addition, (A) the average length of the ridge is set to a value within the range of more than 30 mm to 150 mm.
The reason for this is that when the average length of (A) wrinkles becomes a value of 30 mm or less, when a wrinkle-containing molded product is produced, the horizontal orientation of the wrinkles becomes insufficient, and mechanical strength and surface smoothness are reduced. This is because may decrease significantly.
On the other hand, when the average length of the (A) soot exceeds 150 mm, it may be difficult to uniformly mix and disperse even if a mixing device such as a cement mixer is used.
Accordingly, (A) the average length of the ridge is preferably set to a value within the range of 40 to 140 mm, more preferably set to a value within the range of 50 to 130 mm, and a value within the range of 70 to 120 mm. More preferably.
In addition, (A) If the average length of a ridge is before shaping | molding of a cocoon containing molded product, the length of several ridges will be measured with an optical microscope (including image processing), a caliper, etc., for example, as an average value Can be calculated.
On the other hand, if it is after shaping | molding of a wrinkle containing molded article, in (A) wrinkles in the surface of a wrinkle containing molded article, for example, using a light microscope (including image processing), calipers, etc., and measuring a plurality of lengths, It can also be calculated as an average value.

Here, with reference to FIGS. 1 to 3, (A) the relationship between the average length of ridges and various properties (density, surface hardness, bending strength, etc.) will be described.
That is, in FIG. 1, the horizontal axis represents the average length (mm) of the wrinkles used, and the vertical axis represents the density (kg) of the wrinkle-containing molded product measured according to JIS A 5905. / M ³ ), and FIG. 1 shows characteristic curves (A1 and A1 ′) showing the relationship between them.
The characteristic curve A1 corresponds to the cocoon-containing molded product using the cocoon derived from indica rice, and the characteristic curve A1 ′ corresponds to the cocoon-containing molded product using the cocoon derived from japonica rice. ing.
As understood from these characteristic curves (A1 and A1 ′), the longer the average length of the koji used, the lower the density of the koji-containing molded product, which was derived from Indica rice. It is understood that the tendency is even stronger when using firewood.
Therefore, in order to control to a low density, for example, a value of 700 kg / m ³ or less, the average length of both the case where the cocoon derived from indica rice and the case where the cocoon derived from japonica rice is used are used. It can be said that it is effective to use a cocoon having a thickness exceeding 30 mm.
Further, in order to control to a lower density, for example, a value of 600 kg / m ³ or less, it is effective to use the cocoon derived from indica rice and the cocoon whose average length exceeds 30 mm. I can say that.
In addition, in order to control the density to a lower density, for example, a value of 550 kg / m ³ or less depending on the use, it is effective to use a cocoon derived from indica rice and an average length of 50 mm or more. It can be said that.
In any case, the density of the molded product containing cocoons can be adjusted to a desired range (for example, a value of 550 kg / m ³ or less) by selecting the type of cocoons to be used and the average length (mm) thereof. it can.

FIG. 2 shows the average length (mm) of the wrinkles used on the horizontal axis, and shows the surface hardness (N / m ² ) of the wrinkle-containing molded product on the left axis. In FIG. 2, a characteristic curve (A2) showing the relationship between them is indicated by a solid line.
Moreover, B of the characteristic curve (dotted line) described in FIG. 2 is the relationship between the average length (mm) of rice cake (rice cake derived from Indica rice) and the manufacturing cost (relative value) of the rice cake-containing molded product. Is shown.
That is, as understood from the characteristic curve (A2), it is understood that the surface hardness of the cocoon-containing molded product tends to show a substantially constant value regardless of the average length of the cocoon used. Is done.
Therefore, since the influence of the average length of the wrinkles to be used is small, in order to control to a predetermined surface hardness, for example, a value within the range of 5 to 10 N / m ² , at least the average length exceeds 30 mm. It can be said that a wrinkle of 140 mm or less may be used.
The tendency of the characteristic curve is the same even when japonica rice or the like is used.

On the other hand, as is understood from the characteristic curve (B), when the average length (mm) of the ridges used is relatively short, the manufacturing cost tends to increase rapidly.
This is because, in order to adjust the average length of the wrinkles to be used, the number of times of processing of the cutting machine or the like has to be made a considerable number, but when the number of times of processing of the cutting machine or the like is increased, the yield decreases rapidly. .
For example, if the average length of the wrinkles used is 80 mm or more, the relative value of the manufacturing cost is almost as low as 1. However, if the average length of the wrinkles used is 40 to 60 mm or more, the relative value of the manufacturing cost is 2 When the average length of the ridge used is less than 30 mm, the relative value of the manufacturing cost is significantly increased to 4 to 5.
The manufacturing cost 1 of the soot-containing molded product is about 30 yen per unit area (30 cm × 30 cm), the manufacturing cost 2 is about 50 yen, and the manufacturing cost 3 is about It is about 70 yen, the manufacturing cost 4 is about 80 yen, and the manufacturing cost 5 is about 100 yen.
In any case, by selecting the average length (mm) of the wrinkles to be used, the surface hardness of the wrinkle-containing molded product can be adjusted within a desired range while considering the manufacturing cost of the wrinkle-containing molded product. it can.

FIG. 3 shows the average length (mm) of the wrinkles used on the horizontal axis, and shows the bending strength (MPa) of the wrinkle-containing molded product on the left axis. 3, a characteristic curve (A3) showing the relationship between them is described.
And, as understood from the characteristic curve (A3), the bending strength of the cocoon-containing molded product tends to show a substantially constant value regardless of the average length of the cocoon used (the cocoon derived from indica rice). It is understood that
Therefore, since the influence of the average length of the wrinkles to be used is small, in order to control to a predetermined bending strength, for example, a value within the range of 5 to 15 MPa, at least the average length exceeds 30 mm and is 140 mm or less. It can be said that it is sufficient to use the cocoon of.
The tendency of the characteristic curve is the same even when japonica rice or the like is used.

(3) Average diameter Moreover, it is preferable to make the average diameter of (A) ridge into the value within the range of 1-10 mm.
The reason for this is that when the average diameter of the koji to be blended is less than 1 mm, the handleability may be significantly reduced, or the manufacturing yield when cutting to a predetermined length may be significantly reduced. is there.
On the other hand, when the average diameter of the wrinkles exceeds 10 mm, when the wrinkle-containing molded product is heat-molded, (A) the wrinkles are random or predetermined along the surface direction of the flat wrinkle-containing molded product. This is because it may be difficult to perform horizontal alignment in one direction (one direction) or to stack uniformly. Therefore, good lightness and surface smoothness cannot be obtained, and it may be difficult to laminate a decorative sheet or the like on the surface. Moreover, if the average diameter exceeds 10 mm, part of the wrinkle-containing molded product may be lost or excessive warpage may occur.
Therefore, (A) the average diameter of the ridge is more preferably set to a value within the range of 2 to 8 mm, and further preferably set to a value within the range of 3 to 7 mm.
Note that (A) the average diameter of the soot is an optical microscope for (A) soot alone or (A) soot contained in the soot-containing molded product before and after heat-molding of the soot-containing molded product. The diameter can be measured at a plurality of locations (at least 3 locations) with calipers (including image processing) and the like, and the average value can be calculated.

(4) Surface treatment (hydrophilic treatment)
Moreover, it is preferable that (A) the soot is subjected to at least one surface treatment (hydrophilization treatment) of flame treatment, silicic acid flame treatment, corona treatment, surfactant treatment, and primer treatment.
The reason for this is that by performing the surface treatment (hydrophilization treatment) in this manner, the adhesiveness of the isocyanate-based adhesive with respect to the wrinkles is improved, and a wrinkle-containing molded article having more excellent mechanical strength can be easily obtained. Because.

More specifically, the flame treatment is performed by spraying a flame derived from the fuel gas onto the surface of the solid substance by using a gas burner or the like, so that polar groups such as carboxyl groups are applied to the surface. It is a surface treatment method that is formed and modified to be hydrophilic or easily adhesive.
In addition, the silicic acid flame treatment is performed by spraying a silicic acid flame derived from a fuel gas containing a silicon-containing compound on the surface of the soot by using a gas burner or the like, thereby providing a predetermined number of hydroxyl groups on the surface. This is a surface treatment method in which silica particles are generated firmly and uniformly on the surface to greatly improve hydrophilicity and easy adhesion.
Further, corona treatment is a surface treatment technique for improving hydrophilicity and easy adhesion by irradiating corona discharge to the heel surface.
Furthermore, primer treatment (including surfactant treatment) is a surface treatment technique in which a primer layer made of a polar polymer or the like is formed on the surface of the ridge and modified to hydrophilicity or easy adhesion.
In addition, it is preferable to make the wetting index (surface tension, 25 ° C.) of the wrinkle to be a value of 50 mN / m or more by the surface treatment, and more preferably within a range of 60 to 80 mN / m. More preferably, the value is in the range of 65 to 73 mN / m.

2. Component (B): Type of isocyanate-based adhesive (1) The type of (B) isocyanate-based adhesive is not particularly limited, and includes conventionally known isocyanate compounds and polymers thereof.
More specifically, a butadiene compound having a hydroxyl group (for example, a butadiene-styrene-vinylpyridine terpolymer obtained by grafting a hydroxyl group-containing monomer), a natural rubber having a hydroxy group, as a predetermined main agent. Compounds (for example, natural rubber compounds formed by grafting hydroxyl group-containing monomers), urethane compounds having hydroxy groups, polyester compounds having hydroxy groups, polyolefin compounds having hydroxy groups, polyamide compounds having hydroxy groups, etc. At least one is mentioned.
In particular, grafted with latex of butadiene-styrene-vinylpyridine terpolymer (grafted amount is 0.01 to 0.5% by weight) and grafted with hydroxyl group-containing monomer. Natural rubber compound (graft amount is 0.01 to 0.5% by weight) reacts sufficiently with the curing agent described later, and (A) reacts strongly against soot, It is possible to obtain a wrinkle-containing molded article having excellent mechanical strength, little internal stress, and little warpage.

On the other hand, as a curing agent of a predetermined main agent, aromatic isocyanates and aromatic polyisocyanates such as diphenylmethane diisocyanate (MDI), polymethylene polyphenyl polyisocyanate, tolylene diisocyanate (TDI), naphthalene diisocyanate; hexamethylene diisocyanate (HDI) Aliphatic isocyanates and aliphatic polyisocyanates such as lysine methyl ester diisocyanate; alicyclic isocyanates and alicyclic polyisocyanates such as hydrogenated diphenylmethane diisocyanate, isophorone diisocyanate and hydrogenated tolylene diisocyanate. These can be used alone or in admixture of two or more.
Among these, (A) because it reacts specifically with soot, is highly safe, and is low in price, a butadiene compound having a hydroxy group is used as a main agent, and as a curing agent. It is more preferable to use an isocyanate adhesive which is polymethylene polyphenyl polyisocyanate.

(2) Compounding quantity Moreover, the compounding quantity of (B) isocyanate adhesive is made into the value within the range of 10-200 weight part with respect to (A) 100 weight part of 藁.
The reason for this is that (B) by setting the isocyanate-based adhesive in such a blending amount, the (A) uniform mixing property with the cocoon increases, and when it is thermoformed, the adjacent (A) cocoons are more This is because, since it is firmly bonded, a wrinkle-containing molded product having excellent mechanical strength and less warpage can be obtained.
That is, (A) the hydroxyl group contained in the soot and (B) the polyfunctional isocyanate group in the isocyanate-based adhesive react to form a urethane bond, so that there is no binder resin other than the isocyanate-based adhesive. Even if it is a case, it is because (A) ridges can be firmly adhere | attached through an isocyanate adhesive agent.
Therefore, the omission of (A) soot from a predetermined location (surface edge) of the soot-containing molded product can be effectively prevented after heat-molding the soot-containing molded product.

More specifically, when the blending amount of the (B) isocyanate-based adhesive is less than 10 parts by weight, (A) the uniform mixing with the soot decreases, and the soot-containing molded product is heat-molded. This is because the mechanical strength may be excessively lowered or the handleability as a composition may be difficult.
Moreover, it is because a part of wrinkles may be missing from the plate after processing the obtained wrinkle-containing molded product into a plate shape.
On the other hand, when the blending amount of the (B) isocyanate-based adhesive exceeds 200 parts by weight, warpage may easily occur when processed into a plate shape due to the relationship with (A) ridge. It is.
Therefore, it is more preferable to set the blending amount of the (B) isocyanate-based adhesive to a value within the range of 12 to 100 parts by weight with respect to 100 parts by weight of (A) 藁, and within the range of 15 to 50 parts by weight. More preferably, it is a value.

3. (C) Component: Water (1) Type (B) Adjusting the viscosity of the isocyanate-based adhesive, (A) improving the miscibility with soot, and (A) soot and (B) isocyanate-based In order to promote the chemical reaction with the adhesive, it is preferable to blend a predetermined amount of water as the component (C).
That is, it is preferable to use tap water, natural water, distilled water, pure water, purified water, ion exchange water, alkaline electrolyzed water, industrial water, ground water, well water, soft water, etc. as (C) water.

(2) Compounding quantity Moreover, it is preferable to make the compounding quantity of (C) water into the value within the range of 1-30 weight part with respect to (A) 藁 100 weight part.
This is because (C) by adjusting the amount of water in such a range, it becomes easy to adjust the viscosity of (B) the isocyanate-based adhesive, and (A) the miscibility with soot is further increased. This is because the chemical reaction between (A) cocoon and (B) the isocyanate adhesive can be promoted.
More specifically, when the amount of (C) water is less than 1 part by weight, it becomes difficult to adjust the viscosity of (B) the isocyanate-based pressure-sensitive adhesive, and (A) the miscibility with soot decreases. In addition, the chemical reaction between (A) Ａ and (B) the isocyanate-based adhesive may be insufficient.
On the other hand, when (C) the amount of water exceeds 30 parts by weight, (B) the isocyanate-based adhesive reacts excessively, or the mechanical strength of the resulting soot-containing molded product decreases. Because there is.
Therefore, it is more preferable that the amount of (C) water is within the range of 5 to 20 parts by weight, and more preferably within the range of 8 to 15 parts by weight with respect to 100 parts by weight of (A) straw. .

4). (D1) Component: Fumigant (1) Type It is also preferred that the fumigant-containing composition contains a fumigant as the component (D1) depending on the use of the fumigated molded product.
Here, the type of fumigant is not particularly limited. For example, methyl bromide, ethyl bromide, propyl bromide, methyl iodide, ethyl iodide, propyl iodide, sulfuryl fluoride, phosphorus It is preferably at least one of aluminum halide and propylene oxide.
The reason for this is that, with such a fumigant type, a predetermined fumigation effect can be effectively exhibited in the obtained fumig-containing molded product even with a relatively small amount of blending.
In addition, when the fumigant is not liquid or solid at room temperature but is a gas, it is preferably used in a state dissolved in water, an alcohol compound or the like (for example, a concentration of 1 to 30% by weight).

(2) Compounding amount Moreover, in the soot-containing composition, (D1) the fumigant is further blended so as to have a value within the range of 0.01 to 30 parts by weight with respect to (A) 100 parts by weight of soot. It is preferable.
This is because a rice straw molded product having excellent safety can be obtained by blending a predetermined amount of (D1) fumigant.
More specifically, it is because the fumigation effect may not be exhibited when the blending amount of the (D1) fumigant is less than 0.01 parts by weight.
On the other hand, when the blending amount of the (D1) fumigant exceeds 30 parts by weight, the mechanical strength of the smoke-containing molded product becomes insufficient, the workability decreases, or the This is because the surface smoothness may decrease.
Therefore, it is more preferable that the blending amount of the (D1) fumigant is set to a value within the range of 0.1 to 20 parts by weight with respect to 100 parts by weight of (A) soot. More preferably, the value is within the range.

5. (D2) Component: Flame Retardant (1) Type Depending on the application of the soot-containing molded product, it is preferable that the soot-containing composition contains a flame retardant as the (D2) component.
Here, the type of the flame retardant is not particularly limited, but the flame retardant is a phosphorus flame retardant, a halogen flame retardant, an antimony flame retardant, a water-containing inorganic flame retardant, or a borax flame retardant. It is preferable that it is at least one of these.
The reason for this is that with such a flame retardant, the flame retardancy can be effectively improved even with a relatively small amount.
Moreover, if it is these flame retardants, it will be easy to mix with soot uniformly and the surface smoothness of a soot-containing molded product can be further improved.

(2) Compounding quantity Moreover, it is preferable to make the compounding quantity of (D2) a flame retardant into the value within the range of 10-100 weight part with respect to (A) 藁 100 weight part.
The reason for this is that, if the blending amount of the flame retardant (D2) is a value within such a range, a soot-containing molded article excellent in flame retardancy can be obtained while maintaining predetermined mechanical properties. Because.
More specifically, when the blending amount of the flame retardant (D2) is less than 10 parts by weight, the flame retardant effect may not be exhibited, or the surface smoothness of the soot-containing molded product may be reduced. Because there is.
On the other hand, when the blending amount of (D2) flame retardant exceeds 100 parts by weight, the mechanical strength of the soot-containing molded product is reduced, the workability is reduced, or the surface smoothness of the soot-containing molded product is reduced. This is because there is a case where the property is lowered.
Therefore, it is more preferable to set the blending amount of the flame retardant (D2) to a value in the range of 20 to 80 parts by weight, and a value in the range of 40 to 60 parts by weight with respect to 100 parts by weight of (A) 藁. More preferably.

6). Other Additives In addition, as a colorant for the cocoon-containing composition, (A) 100 parts by weight of cocoon is 0.1 It is preferable to blend various pigments and dyes in the range of 30 parts by weight.
Furthermore, in order to improve various properties of the soot-containing molded product or to impart a predetermined functionality, the soot-containing composition has an ultraviolet absorber, an antioxidant, a combustion energy improver, a fiber, It is also preferable to blend at least one of an additive composed of a lightening agent, an extender, metal particles, inorganic particles, ceramic particles, and organic particles.

7). Thermoforming conditions (1) Temperature In addition, it is preferable to set the temperature at the time of thermoforming the soot-containing composition to a value within the range of 150 to 180 ° C.
The reason for this is that by setting such a temperature condition, the mixing property between (A) cocoon and (B) isocyanate-based adhesive can be made uniform, and the cocoon-containing molded product can be made to have a relatively large area. This is because even when it is thermoformed into a plate shape, the internal distortion is small, and the occurrence of warping with the passage of time can be reduced.
More specifically, when the temperature at the time of thermoforming is less than 150 ° C., the chemical reaction between (A) the hydroxyl group contained in the soot and (B) the isocyanate group contained in the isocyanate-based adhesive is insufficient. This is because the mechanical strength at the time of heat forming into a plate shape may be significantly reduced.
Moreover, the removal of water becomes insufficient, and the mechanical strength of the obtained soot-containing molded product may further decrease, or corrosion may occur after being heat-molded into a plate shape.
On the other hand, when the temperature at the time of heat forming exceeds 180 ° C., the internal distortion of the obtained soot-containing molded product increases, and warping may easily occur in use.
Therefore, the temperature at the time of thermoforming is more preferably set to a value within the range of 155 to 175 ° C, and further preferably set to a value within the range of 160 to 170 ° C.
In addition, when using a hot press apparatus etc., the temperature at the time of thermoforming can be defined as the surface temperature of the pressurization surface, and can be measured using a thermocouple or an infrared temperature sensor.

(2) Pressure Moreover, it is characterized by making the pressure at the time of heat-molding a soot-containing composition into the value within the range of 2-100 kgf / cm < ² >.
The reason for this is that by using such a pressure condition, the mixing property between (A) 藁 and (B) the isocyanate-based adhesive can be made uniform, and as a result, uniformly in a plate shape. This is because it can be molded, and the occurrence of internal distortion in the obtained wrinkle-containing molded product is reduced, and as a result, the occurrence of warpage can be reduced.

More specifically, when the pressure at the time of heat forming becomes a value of less than 2 kgf / cm ² , uniform mixing of (A) cocoon and (B) isocyanate-based adhesive becomes difficult or obtained. This is because the mechanical strength of the contained molded product may be excessively lowered or warped.
Moreover, when the pressure at the time of heat forming becomes a value of less than 2 kgf / cm ² , the compression becomes insufficient, and soot may be missing from the obtained soot-containing molded product after being processed into a plate shape. is there.
On the other hand, when the pressure at the time of heat forming exceeds 100 kgf / cm ² , when processing into a plate shape, the internal distortion of the obtained soot-containing molded product increases, and warpage tends to occur. Because there is.
Therefore, it is more preferable to set the pressure at the time of heat-molding the soot-containing composition to a value within the range of 5 to 50 kgf / cm ² , and further preferably to a value within the range of 10 to 30 kgf / cm ² .
In addition, the pressure at the time of thermoforming means the pressurization force per unit area, when using a hot press apparatus etc., and can be confirmed using a pressure gauge etc.

(3) Time In addition, it is preferable to set the time when heat-molding the soot-containing composition to a value within the range of 1 to 60 minutes.
The reason for this is that when the pressure-bonding time is set as described above, the chemical reaction between (A) 藁 and (B) the isocyanate-based adhesive can be sufficiently promoted, and when it is molded into a plate shape. This is because the resulting warp-containing molded product has less internal distortion and less warpage.

More specifically, when the time for heat forming becomes a value of less than 1 minute, the chemical reaction between (A) cocoon and (B) the isocyanate-based adhesive becomes insufficient or is obtained. This is because the mechanical strength of the contained molded product may be excessively reduced or part of the wrinkles may be lost.
Moreover, it is because removal of water becomes inadequate and the mechanical strength of the obtained soot-containing molded product may fall.
On the other hand, when the time for heat forming exceeds 60 minutes, the yield of the soot-containing molded product decreases, or the internal strain of the resulting soot-containing molded product increases when processed into a plate shape. This is because warpage is likely to occur.
Therefore, it is more preferable to set the time for heat forming to a value within the range of 3 to 30 minutes, and it is even more preferable to set the value within the range of 5 to 20 minutes.
As will be described later, when heat forming using a press device or the like, by using high-frequency heating, uniform and quick heating from the inside becomes possible, compared with the case where high-frequency heating is not used together. In addition, the heating time can be considerably shortened, and further, the effect of further suppressing the occurrence of warpage of the obtained soot-containing molded product can be obtained.

(4) Manufacturing apparatus Moreover, it does not restrict | limit especially as an apparatus at the time of heat-molding a wrinkle containing composition and manufacturing a wrinkle containing molded article, It is using a well-known hot press apparatus, an extrusion apparatus, etc. it can.
Moreover, in the case of this invention, since water is mix | blended, it is preferable to use an open type press apparatus.
On the other hand, when producing a soot-containing molded product by thermoforming with a press device or the like, high frequency heating, for example, oscillation frequency is 13.56 MHz, anode current is 0.5 to 5 A, and high frequency output is 0.5 to 5 kW. It is preferable to apply a high frequency under conditions and use together with heating.
The reason for this is that uniform and rapid heating from the inside becomes possible by using the high-frequency heating together.
Therefore, when high-frequency heating is used in combination, the time for heat-molding can be shortened to about 1/2 to 1/5 as compared with the case where high-frequency heating is not used together.
In addition, when combined heating is performed, the mixing ratio and reaction status of the wrinkles on the upper surface and the lower surface of the wrinkle-containing molded product, which is the pressure surface, and the isocyanate-based adhesive are made uniform, and the effect of further suppressing the occurrence of warpage, etc. Can be obtained.

(5) Volumetric compressibility It is also preferable that the volumetric compressibility at the time of producing the soot-containing molded product by heat-molding the soot-containing composition is a value within the range of 12 to 90%.
The reason for this is that by setting the volume compressibility to such a value, the mixing property between (A) 藁 and (B) the isocyanate-based adhesive can be made uniform, and in the form of a plate. This is because, when molded, the resulting warp-containing molded product has less internal distortion, less warpage, and less wrinkles from the soot-containing molded product.
That is, when the initial volume at the time of heat molding is Acm ³ and the volume of the obtained soot-containing molded product is Bcm ³ , volume compression represented by [(AB) / A × 100)] (%) The rate (%) is preferably set to a value within a predetermined range.

More specifically, when the volumetric compressibility is less than 12%, the residual moisture and the like are relatively large, and the mechanical strength of the obtained soot-containing molded product decreases when processed into a plate shape. This is because warpage is likely to occur or part of the wrinkle is likely to be lost from the wrinkle-containing molded product.
On the other hand, if the volumetric compression ratio exceeds 90%, the yield of the soot-containing molded product is reduced, or the internal strain of the soot-containing molded product to be obtained becomes large when warped and processed into a plate shape. This is because it may be easy to occur.
Therefore, it is more preferable to set the volumetric compression rate during heat molding to a value within the range of 20 to 80%, and it is even more preferable to set the volumetric compression rate to a value within the range of 30 to 60%.

8). Formability / Various Properties (1) Thickness Further, regarding the form of the wrinkle-containing molded product, as shown in FIG. 7, the wrinkle-containing molded product 10 is plate-shaped, and the average thickness of the wrinkle-containing molded product is 3 A value in the range of ˜50 mm is preferable.
The reason for this is that a plate-like wrinkle-containing molded product having relatively little warpage and uniform bending strength, water absorption, etc. can be stably obtained by using a wrinkle-containing molded product having such a thickness. It is because it can do.
Therefore, the average thickness of the soot-containing molded product is more preferably set to a value within the range of 10 to 40 mm, and further preferably set to a value within the range of 15 to 30 mm.
In addition, when the wrinkle-containing molded product is plate-shaped and the average thickness is 30 mm or more, the average thickness is relatively thin, for example, a plurality of wrinkle-containing molded products having an average thickness of 5 to 10 mm in advance. It is also preferable to prepare in advance, or to prepare in advance such a semi-cured soot-containing molded product having an average thickness.
And, the average thickness is relatively thin, a plurality of wrinkle-containing molded products, or a plurality of semi-cured wrinkle-containing molded products, and further, in a state where a plurality of these combinations are stacked, By performing the lamination process again under the heating and pressurizing conditions described above, for example, an average thickness of 30 mm or more can be obtained, and a more uniform soot-containing molded product can be obtained.
For example, in a state in which a semi-cured wrinkled molded product having an average thickness of 15 mm is sandwiched between plate-shaped wrinkled molded products having an average thickness of 10 mm, for example, 150 to 180 ° C., 2 to 100 kgf / Cm < ² >, It can be set as the plate-shaped soot-containing molded article of average thickness 33mm by pressurizing on the lamination | stacking conditions for 1 to 60 minutes.

(2) Shape Moreover, although it does not restrict | limit also especially about the shape of a wrinkle containing molded article, For example, it is also preferable that the planar shape is made into a square or a rectangle.
This is because such a shape is standardized, so it is easy to form various products derived from cocoon-containing molded products, and can be easily and accurately spread on floors and walls. is there.
Alternatively, it is also preferable that the shape (planar shape) of the bag-containing molded product is a triangle, a pentagon, a circle, an ellipse, an irregular shape, a long shape, a perforated shape, or the like depending on the use application.

(3) Modification 1
Further, the combination of the soot-containing molded product and the other layered product is not particularly limited. For example, as shown in FIG. 7B, at least one surface of the soot-containing molded product 10 is protected. It is preferable that the sheets 10c and 10d are laminated to form a decorative bag-containing molded product 10 ′.
The reason for this is that by laminating the protective sheets 10c and 10d, it is possible to prevent scattering of small pieces of cocoons contained in the cocoon-containing molded product, and to improve mechanical properties and surface smoothness. Also, the storability can be enhanced as desired.

Here, as the protective sheet laminated on the surface of the bag-containing molded product, for example, fabrics such as woven fabrics, knitted fabrics, and nonwoven fabrics made of various fibers; single-piece made of vinyl chloride resins, olefin resins, thermoplastic elastomers, and the like. A synthetic resin sheet having a layer or a plurality of layers; a so-called synthetic resin leather in which a vinyl chloride resin layer or a thermoplastic elastomer layer is formed on the surface of the fabric; artificial leather; a flocked sheet in which fiber flocks are implanted on the surface of the fabric; or these The laminated sheet etc. are mentioned.
Furthermore, it is also preferable that surface treatment such as embossing is performed on the outer surface of the protective sheet for the purpose of improving decoration, improving mechanical properties, or matting.
Therefore, the type of the protective sheets 10c and 10d can be appropriately changed depending on the use. For example, polyester film, olefin film, acrylic film, urethane film, vinyl chloride film, rubber material film, epoxy film, ceramic film, etc. At least one is preferred.

(4) Modification 2
Moreover, as shown in FIG.7 (c), it is also preferable to laminate | stack the decorative sheet | seat 10c on the at least 1 surface of the cage | basket containing molded article 10, and to make the ornamental cage containing molded article 10 ''.
The reason for this is that the cocoon-containing molded product of the present application can be used as a building material with excellent design and decorative properties, such as flooring and wall materials, or furniture by laminating decorative sheets to form a decorative cocoon-containing molded product. This is because it can be used as a material.
In other words, if it is a molded article containing decorative candy, it is more environmentally safe and difficult as an alternative to medium density fiberboard (MDF) or high density fiberboard (HDF), which is conventionally used as a building material and furniture material. It can be used as a floor material, wall material, furniture material or the like having excellent flammability.

Here, as a decorative sheet laminated on the surface of the bag-containing molded product, for example, on a base material such as a polyester film, an olefin film, etc., an aspect in which characters, figures, symbols, etc. are formed using a known printing device. More specifically, it is also preferable that an arbitrary pattern such as a background color and a different color pattern of the decorative sheet, or a wood grain pattern is printed on the surface of the decorative sheet.
Furthermore, a decorative sheet provided with an ultraviolet resistant function or an antistatic function may be used.
In addition, it is also preferable that surface processing such as embossing is performed on the outer surface of the decorative sheet for the purpose of improving decoration, improving mechanical properties, or matting.

(4) Bending strength Moreover, it is preferable to make the bending strength of the wrinkle containing molded article measured based on JIS A 5905 into the value within the range of 1-100 Mpa.
This is because a wrinkle-containing molded product with less warpage and excellent durability and mechanical strength can be obtained by using a wrinkle-containing molded product having such bending strength.

More specifically, when the bending strength becomes a value of less than 1 MPa, the durability as a flaw-containing molded product is excessively lowered, or is firmly fixed using a connection member (nail, bolt, metal fitting, etc.). This may be difficult.
On the other hand, when the bending strength exceeds 100 MPa, warping may increase or workability may decrease with time.

Therefore, it is more preferable to set the bending strength of the wrinkle-containing molded product to a value within the range of 5 to 50 MPa, and even more preferable to set the value within the range of 8 to 20 MPa.
In addition, the obtained soot-containing molded product may contain voids (voids) in addition to blending components such as soot and isocyanate-based adhesives. However, if there are too many such pores, Although the weight, that is, the lightness is improved, the value of the bending strength described above is lowered, and as a result, the mechanical strength may be excessively lowered.
Therefore, even if it contains voids, it is preferably 40% or less per unit volume (100%) of the soot-containing molded product, more preferably 0.1 to 30%, Preferably it is 1 to 20%.

(5) Moisture content Moreover, it is preferable to make the moisture content measured based on JISK7209 of a soot-containing molded article into the value within the range of 0.01 to 10%.
The reason for this is to obtain a wrinkle-containing molded article with less warpage and excellent durability, mechanical strength, or electrical properties (low dielectric constant) by using a wrinkle-containing molded article having such a moisture content. Because it can.

More specifically, when the moisture content is less than 0.01%, the processability of the soot-containing molded product may be excessively lowered.
On the other hand, when the moisture content exceeds 10%, warping may become excessively large with time, mechanical strength may decrease, or quality may easily decrease. .
Therefore, the moisture content of the soot-containing molded product is more preferably set to a value in the range of 1 to 8%, and further preferably set to a value in the range of 2 to 6%.

(6) Density Moreover, it is preferable to make the density of the wrinkle containing molded article measured based on JIS A 5905 into the value within the range of 0.2-1.2 g / cm < ³ >.
This is because a wrinkle-containing molded product having a light weight and excellent handleability can be obtained by using a wrinkle-containing molded product having such a density.
More specifically, when the density is less than 0.2 g / cm ³ , the mechanical strength and workability of the wrinkle-containing molded product may be excessively reduced.
On the other hand, when the density exceeds 1.2 g / cm ³ , the lightness may be reduced, and warping may become excessively large with time.
Therefore, it is more preferably set to a value within the range of density straw containing moldings 0.3 to 0.8 g / cm ^3, a value within a range of 0.4 to 0.6 g / cm ³ Further preferred.

(7) Flame retardancy In addition, the flame-containing molded product is a surface test method measured according to JIS A 1321 (1992) building interior materials and method flame retardancy test method, equivalent to flame retardant grade 2 It is preferable to exhibit the above flame retardancy.
The reason for this is that it is a predetermined standard for flame retardancy of molded products containing soot, and on the other hand, it does not contain any binder resin other than isocyanate-based adhesives. This is because the surface test method measured according to the property test method can easily exhibit flame retardancy equal to or higher than that of the flame retardant grade 2.

[Second Embodiment]
In the second embodiment, a cocoon-containing composition containing (A) cocoon and (B) an isocyanate-based adhesive is formed into a predetermined shape by thermoforming, and (A) the cocoon is horizontally oriented. It is a manufacturing method of a wrinkle containing molded article, Comprising: It is a manufacturing method of the wrinkle containing molded article characterized by including the following process (1)-(3).
(1) Cutting the raw material cocoons so that the average length becomes a value in the range of more than 30 mm to 150 mm to obtain (A) cocoon having a predetermined length (2) (A) 100 parts by weight of cocoon In contrast, (B) an isocyanate-based adhesive is blended so as to have a value within a range of 10 to 50 parts by weight, and (C) water is blended so as to have a value within a range of 10 to 30 parts by weight, thereby creating a soot-containing composition. Step (3) Heat-molding the soot-containing composition under conditions of 150 to 180 ° C. and ^{2 to} 100 kgf / cm ² , the thickness is in the range of 3 to 50 mm, and (A) soot is A thermoforming process for producing a cocoon-containing molded product characterized in that it is horizontally oriented in a random direction or a predetermined direction along the horizontal direction of the flat cocoon-containing molded product. The manufacturing method of a wrinkle containing molded product is demonstrated along (a)-(f).

1. Step 1: Cutting Step As shown in FIG. 9A, Step 1 is a step of cutting the raw material ridges into a predetermined length of (A) ridges having an average length of 50 to 150 mm. is there.
Here, the apparatus for cutting the raw material scissors is not particularly limited as long as it can be cut to a predetermined length, and examples thereof include a cutting machine, a press cutter, a chopper, a knife, and a cutter.

2. Step 2: Manufacturing Process of Soot-Containing Composition Next, as shown in FIG. 9 (b), the process 2 includes (A) soot and (B) an isocyanate-based adhesive, and (C) water as required. It is the process of mixing uniformly after each mix | blending and setting it as a soot-containing composition.
Moreover, when (D1) a fumigant and (D2) a flame retardant are mix | blended, in process 2, it is preferable to prepare these additives, respectively, and to mix uniformly with respect to a soot-containing composition.
That is, in step 2, at least (A) 100 parts by weight of (A) is blended with (B) an isocyanate-based adhesive so as to have a ratio in the range of 10 to 200 parts by weight, until it is uniform. It is a process of mixing and creating a predetermined soot-containing composition.

Here, after blending (B) an isocyanate-based adhesive, (C) water, etc. into a container with a stirrer, for example, a cement mixer or a planetary mixer, (B) isocyanate using a stirrer System adhesive and (C) water and the like are mixed uniformly to adjust the viscosity of the isocyanate adhesive, then (A) fumigation and, if necessary, fumigant, flame retardant, etc. are blended sequentially, It is preferable to mix until uniform.
In addition, about the content of (A) soot, (B) isocyanate adhesive, (C) water, (D1) fumigant, and (D2) flame retardant, or those mixture ratios, it is 1st Embodiment. Since it demonstrated, the description here is abbreviate | omitted.

3. Step 3: Molding process of soot-containing molded product Next, as shown in FIG. 9 (c), the process 3 is performed by subjecting the soot-containing composition obtained in Step 2 to heating and pressing conditions (high frequency) at a predetermined temperature and a predetermined pressure. In some cases, heating is used in combination.) To form a soot-containing molded product having a predetermined shape, and to evaporate moisture.
More specifically, a thermoforming process is performed, and a soot-containing composition comprising at least (A) soot, (B) an isocyanate-based adhesive, and (C) water is used at 150 to 180 ° C. and 2 to 100 kgf. It is preferable to heat mold under the conditions of / cm ² .
That is, by performing a heat treatment or the like while applying pressure under such conditions, (A) to obtain a molded article containing cocoons with less mechanical stress and excellent mechanical strength while maintaining the shape of the cocoons. Can do.
And in implementation of this thermoforming process, as mentioned above, when forming in flat form (plate shape) etc., it is suitable to use a heat press apparatus etc. provided with a seal type or an open mold. It is also preferable to use a sealed or unsealed kneader or an extrusion device.
In addition, in the metal mold | die in a hot press apparatus etc., before heating and pressurizing a soot containing composition, it is preferable to include the process of rocking | fluctuating or providing an ultrasonic vibration and smoothing the surface.
This is because even a large-area plate-shaped rice bran-containing molded product can be heated and pressed uniformly in a short time by flattening the surface as the raw material in advance.

4). Cooling Step and Inspection Step (1) Cooling Step Next, although it is an optional step, it is preferable to carry out a cooling step for the soot-containing molded product as shown in FIG.
In other words, while maintaining the pressurizing conditions of a hot press device, etc., it is a step of blowing cold air or the like to cool the mold to a predetermined temperature and suppressing the occurrence of bending deformation or the like due to the internal stress of the bag-containing molded product .
Note that it is not always necessary to cool to room temperature. If the temperature is lowered to about 100 ° C., after that, it is naturally cooled with no pressure applied or at a low pressure, for example, 20 Kgf / cm ^2. Is also preferable.

(2) Inspection Step Next, although this is also an optional step, as shown in FIG. 9 (e), it is preferable to carry out an inspection step for the obtained soot-containing molded product.
That is, it is preferable to confirm that the predetermined inspection conditions are satisfied by actually measuring or visually observing the bending strength, density, width, thickness, moisture content, and the like of the wrinkle-containing molded product.

5. Additional Step Next, although it is an optional additional step, it is preferable to perform a step of further laminating a decorative sheet on the bag-containing molded product as shown in FIG. 9 (f).
That is, it is a step of laminating a decorative sheet on at least one surface of the obtained cocoon-containing molded product via a known adhesive or pressure-sensitive adhesive to process it into a building material, furniture material, or the like.
In addition, this additional process may be implemented before the above-mentioned inspection process, and you may implement an inspection process again after a lamination process.
And since the content of the decoration sheet was demonstrated in 1st Embodiment, description here is abbreviate | omitted.

On the other hand, as another additional process, it is also preferable to assemble a transportation pallet as shown in FIGS. 8A to 8C based on the obtained soot-containing molded product.
In such an additional process, the entire product including the top plate 12 and the legs 14 of the transporting pallet 20 as shown in FIGS. 8A to 8C is configured using the obtained soot-containing molded product. You can also
Alternatively, in consideration of manufacturing cost, mechanical strength, and usability, only the top plate 12 portion or only the leg portion 14 of the transport pallet 20 is configured using the obtained bag-containing molded product. You can also.

  Hereinafter, the present invention will be described in more detail by way of examples. However, the following description shows the present invention by way of example, and the present invention is not limited to these descriptions.

[Example 1]
1. Process 1
200 Kg of rice straw (derived from Indica rice) as agricultural waste is stored in a cutting machine (chopper), which is a cutting device, cut, and fired with an average length of 50 mm and an average diameter of 5 mm (referred to as TYP1 in the table) .) Was collected in a predetermined amount.

2. Process 2
Next, 400 g (100 parts by weight) of the cut TYP1 cake (A) was accommodated in a cement mixer, and then 10 g (2.5 parts by weight) of water was added while stirring at a rotation speed of 60 rpm.
Next, after confirming that the whole rice straw was moistened, 80 g (20 parts by weight) of an isocyanate-based adhesive (Sumitomo Forestry Crest, Hardener U-1, in Table 1, referred to as TYPA) was blended, Further, the rice bran-containing composition was prepared by mixing and stirring for 3 minutes with a stirrer.

3. Process 3
About the obtained rice bran containing composition, it heat-molded so that it may become a volume compressibility of about 80% on 180 degreeC, 4.8 kgf / cm < ² >, and the crimping | compression-bonding conditions for 15 minutes using a sealing-type hot press apparatus. A plate-shaped rice bran-containing molded product having a square planar shape and an average thickness of 15 mm was prepared.

4). Evaluation of rice bran and rice bran-containing molded products (1) Horizontal orientation (Evaluation 1)
The horizontal orientation of rice straw in the obtained rice straw-containing molded product was evaluated by visually observing the side surface of the rice straw-containing molded product according to the following criteria.
A: 90% or more of the whole rice straw is horizontally oriented.
○: 60% or more of the whole rice straw is horizontally oriented.
Δ: 30% or more of the whole rice straw is horizontally oriented.
X: Less than 30% of the whole rice straw is horizontally oriented.

(2) Evaluation of bending strength (Evaluation 2)
With respect to the obtained wrinkle-containing molded product, (A) a measurement sample in a state in which wrinkles are substantially aligned in the horizontal direction is cut out, the bending strength measured in accordance with JIS A 5905 is measured, and the following criteria are used: The bending strength was evaluated.
A: The bending strength is a value of 8 to 20 MPa.
○: The bending strength is less than 8 MPa or more than 20 MPa.
(Triangle | delta): It is a value whose bending strength is less than 2 MPa or exceeds 50 MPa.
X: The bending strength is less than 1 MPa or more than 100 MPa.

(3) Surface smoothness (Evaluation 3)
After applying 50 μg of a commercially available two-component elastic adhesive PM200 (manufactured by Cemedine Co., Ltd.) to the surface of the obtained wrinkle-containing molded product, a 200 μm-thick polyester sheet is laminated as a decorative sheet, with a decorative sheet A soot-containing molded product was obtained.
Subsequently, the surface roughness (Ra) of the obtained decorative sheet-containing molded product with a decorative sheet is measured according to JIS B 0601 (1982) by using a surface roughness measuring instrument Surf Test SJ-310 (manufactured by Mitutoyo Corporation). And measured according to the following criteria.
A: Surface roughness (Ra) is a value of 100 μm or less.
A: The surface roughness (Ra) is a value of more than 100 μm and 500 μm or less.
Δ: Surface roughness (Ra) is a value of more than 500 μm and 1000 μm or less.
X: The surface roughness (Ra) is a value exceeding 1000 μm.

(4) Evaluation of density (Evaluation 4)
The obtained soot-containing molded product was cut into a predetermined size and used as a measurement sample, the density measured according to JIS A 5905 was measured, and the density was evaluated according to the following criteria.
A: The density is a value of 0.5 kg / m ³ or less.
A: The density is a value exceeding 0.5 kg / m ³ and 0.8 kg / m ³ or less.
Δ: The density exceeds 0.8 kg / m ³ and is 1.2 kg / m ³ or less.
X: The density is a value exceeding 1.2 kg / m ³ .

(5) Surface hardness (Evaluation 5)
The density measured according to JIS A 5905 was measured for the obtained wrinkle-containing molded product (however, the thickness was 15 mm), and the density was evaluated according to the following criteria.
As a result, it was confirmed that the load had a good Brinell hardness of 1.8 MPa at a load of 18.4 N.

(6) Decorative (Evaluation 6)
The decorativeness of the surface of the obtained wrinkle-containing molded product was evaluated according to the following criteria.
(Double-circle): The pattern derived from a cocoon is observed clearly.
○: The pattern derived from the cocoon is almost clearly observed.
(Triangle | delta): The pattern derived from the cocoon is observed a little clearly.
X: The pattern derived from a cocoon is not observed clearly.

(7) Parasiticity of pests (evaluation 7)
The parasitic state by the pests in the obtained cocoon-containing molded product was observed using an optical microscope, and the parasitic nature of the pests was evaluated according to the following criteria.
(Double-circle): Parasitism by a pest is not observed at all.
○: Parasitism caused by pests is hardly observed.
Δ: Some infestation by pests is observed.
X: Parasitism by a pest is observed remarkably.

[Example 2]
In Example 2, instead of 100 parts by weight of (A) Ａ of TYP1 of Example 1, 100 parts by weight of cocoon (referred to as TYP2 in the table) having an average length of 40 mm and an average diameter of 5 mm was used. In the same manner as in Example 1, a plate-like ridge-containing molded product having an average thickness of 15 mm was obtained and evaluated.

[Example 3]
In Example 3, instead of 100 parts by weight of (A) の of TYP1 of Example 1, 80 parts by weight of (A) Ｔ of TYP1, and 藁 having an average length of 80 mm and an average diameter of 5 mm (referred to as TYP3 in the table) .) Was used in combination with 20 parts by weight, and a plate-like soot-containing molded article having an average thickness of 20 mm was obtained and evaluated in the same manner as in Example 1 except that two types of composite glazes were used.

[Example 4]
In Example 4, instead of 100 parts by weight of TYP1 (A) of Example 1, 80 parts by weight of TYP1 (A), 15 parts by weight of TYP2 (A), and (A) of TYP3 Except for using 5 parts by weight in combination and using three types of composite glazes, a plate-like wrinkle-containing molded product having an average thickness of 30 mm was obtained and evaluated in the same manner as in Example 1.

[Example 5]
In Example 5, the composite glaze of Example 3 was used instead of (A) 100 parts by weight of TYP1 of Example 1, and 1 part by weight of methyl bromide as a fumigant was added in Step 2. In the form of a plate having an average thickness of 20 mm, except that it was mixed in 10 g of water and the amount of the isocyanate adhesive (TYPA) was 15 parts by weight with respect to 100 parts by weight of the composite glaze. A soot-containing molded product was obtained and evaluated in the same manner as in Example 1.

[Example 6]
In Example 6, the composite glaze of Example 3 was used in place of 100 parts by weight of (A) soot of TYP 1 of Example 1, and phosphorous was used as a flame retardant with respect to 100 parts by weight of the composite glaze. A composite flame retardant composed of 120 g (30 parts by weight) of ammonium dihydrogen acid, 80 g (20 parts by weight) of ammonium bromide, and 20 g (5 parts by weight) of guanidine sulfamate resin was blended and adhered Except that the amount of the agent (TYPA) used was 30 parts by weight with respect to 100 parts by weight of (A), and the wrinkle-containing composition was prepared, a plate-shaped wrinkle-containing molded product having an average thickness of 20 mm was obtained. Evaluation was performed in the same manner as in Example 1.

[Example 7]
In Example 7, a silane coupling agent treatment with γ-aminopropyltriethoxysilane (5 g) in step 1 so that hydrophilicity is exerted on the surface of (A) 藁 (TYP1) having an average length of 50 mm or the like. (A) 藁 (TYP1 ′), and in the step 2, it was used, and the amount of the adhesive (TYPA) used was 12.5 parts by weight with respect to 100 parts by weight of (A) 藁Except for the above, in the same manner as in Example 1, a plate-shaped wrinkle-containing molded product having an average thickness of 20 mm was obtained and evaluated.

[Example 8]
In Example 8, a rice bran-containing composition similar to that in Example 3 was prepared, and a semi-cured state was obtained at 180 ° C., 4.8 kgf / cm ² for 2 minutes using a sealed hot press machine. A plate-shaped molded product containing rice straw was prepared.
Subsequently, the same rice bran-containing composition as in Example 3 was additionally charged onto the semi-cured plate-shaped rice straw-containing molded product in a heat press apparatus.
Subsequently, the plate-shaped rice bran-containing molded product in a semi-cured state and the additional rice straw-containing composition were heat-molded at 180 ° C., 4.8 kgf / cm ² for 15 minutes, and the average thickness was 30 mm. A plate-shaped rice bran-containing molded product was prepared and evaluated.

[Comparative Example 1]
In Comparative Example 1, a cocoon-containing composition was prepared using cocoons (referred to as TYP4 in the table) having an average length of 25 mm and an average diameter of 5 mm instead of 100 parts by weight of (A) cocoon of TYP1 of Example 1. Except for the above, in the same manner as in Example 1, a wrinkle-containing molded product having an average thickness of 15 mm was obtained and evaluated.

[Comparative Example 2]
In Comparative Example 2, a cocoon-containing composition was prepared using cocoons (referred to as TYP5 in the table) having an average length of 10 mm and an average diameter of 5 mm instead of 100 parts by weight of (A) cocoon of TYP1 of Example 1. Except for the above, in the same manner as in Example 1, a wrinkle-containing molded product having an average thickness of 15 mm was obtained and evaluated.

[Comparative Example 3]
In Comparative Example 3, in addition to TYP4 wrinkles, a predetermined amount of long fibers derived from kenaf bast was used, and the amount of adhesive (TYPA) used was 100 parts by weight with respect to 100 parts by weight of TYP4 wrinkles. Except for the above, a wrinkle-containing molded product having an average thickness of 15 mm was obtained and evaluated in the same manner as Example 1.

[Comparative Example 4]
In Comparative Example 4, a wood-based chip was used in a predetermined amount in addition to the TYP4 wrinkle, and a wrinkle-containing composition was prepared using a phenolic adhesive (referred to as TYPB in Table 2) as an adhesive. In the same manner as in Example 1, a wrinkle-containing molded product having an average thickness of 15 mm was obtained and evaluated.

According to the wrinkle-containing molded product of the present invention and the method for producing the wrinkle-containing molded product, at least the (A) wrinkle adjusted to a predetermined length and (B) the isocyanate-based adhesive have a predetermined ratio. After uniform blending, by heating and molding under predetermined conditions, a relatively large amount of wrinkles, that is, conversely, even if the blending amount of the adhesive component is 20% by weight or less, uniform horizontal orientation is achieved. It became so.
Therefore, a comparatively thick wrinkle-containing molded product that is extremely inexpensive and has excellent mechanical properties, surface smoothness, and the like can be obtained efficiently.
Therefore, according to the present invention, it is possible to provide a wrinkle-containing molded article excellent in not only mechanical strength but also surface smoothness and the like, and an efficient method for producing such a wrinkle-containing molded article. It was.

In addition, according to the present invention, natural wood, natural objects (kenaf), and the like are practically not included. Therefore, even when the predetermined fumigation treatment is omitted or the fumigation treatment conditions are shortened, there is no infestation caused by pests. It became possible to contain molded products.
Furthermore, according to the present invention, a coloring agent can be blended or a decorative layer or the like can be further formed on the surface according to the application, and the design property is maintained while maintaining excellent mechanical strength. As an excellent soot-containing molded product, it can be used for various applications.
Accordingly, the bag-containing molded product of the present invention can be suitably used for inexpensive building materials, crane transportation platforms (pallets), container materials, furniture materials, and the like.

10, 10 ', 10 ": Mold containing product 10a: Bowl 10b: Binder (isocyanate adhesive)
10c, 10d: protective film 10e, 10f: decorative film with base material 12: top plate 12a: fastener (nail, bolt, etc.)
14: Leg 20: Mount (pallet)

Claims (8)

According to the present invention, there is provided a flat plate-like mold-containing molded product obtained by heat-molding a bag-containing composition containing (A) bag, (B) an isocyanate-based adhesive, and (C) water. ,
(A) For 100 parts by weight of basket
(B) The amount of the isocyanate-based adhesive is set to a value within the range of 10 to 50 parts by weight,
(C) The amount of water is set to a value within the range of 1 to 30 parts by weight,
(A) The average length of the ridges is a value within the range of more than 30 mm to 150 mm,
The thickness of the flat plate-like ridge-containing molded product is a value within the range of 10 to 50 mm,
And (A) The wrinkle-containing molded product characterized in that the wrinkles are horizontally oriented in a random direction or a predetermined direction along the surface of the flat plate-shaped wrinkle-containing molded product.   2. The rice bran-containing molded article according to claim 1, wherein the rice cake (A) is derived from rice straw after harvesting indica rice. The density measured according to JIS A 5905 is set to a value of 550 kg / m ³ or less, soot-containing molded article according to claim 1 or 2. The surface hardness measured according to JIS A 5905 is set to a value within the range of 1 to 50 N / mm ² , soot-containing molded product according to any one of claims 1 to 3.   The wrinkle-containing molded article according to any one of claims 1 to 4, wherein a bending strength measured in accordance with JIS A 5905 is set to a value within a range of 1 to 100 MPa.   The (B) isocyanate-based adhesive includes a butadiene having a hydroxy group as a main agent and an isocyanate compound as a curing agent, and (B) an isocyanate-based adhesive with respect to 100 parts by weight of (A) In a range of 10 to 200 parts by weight, The soot-containing molded product according to any one of claims 1 to 5.   The soot-containing molded article according to any one of claims 1 to 6, wherein the soot-containing composition further comprises (D1) a fumigant and (D2) a flame retardant, or any one of them. (A) It is a manufacturing method of the flat-shaped wrinkle containing molded product which formed the wrinkle containing composition containing a flaw, (B) isocyanate adhesive, and (C) water by heat-molding, Comprising: A method for producing a wrinkle-containing molded article comprising steps (1) to (3).
(1) A step of cutting the raw material cocoons so that the average length becomes a value in the range of more than 30 mm to 150 mm to obtain (A) cocoon having a predetermined length (2) (A) 100 parts by weight of cocoon In contrast, the (B) isocyanate-based adhesive is blended so as to have a value within the range of 10 to 200 parts by weight, and the (C) water is blended so as to have a value within the range of 1 to 30 parts by weight. Step (3) for producing a product The above-mentioned soot-containing composition is thermoformed under conditions of 150 to 180 ° C. and ^{2 to} 100 kgf / cm ² , and the thickness is within a range of 10 to 50 mm, and (A ) Heat forming step for forming a wrinkle-containing molded product, wherein wrinkles are horizontally oriented in a random direction or a predetermined direction along the surface of the flat plate-shaped wrinkle-containing molded product