JP5521308B2 - Flame retardants - Google Patents

Description

  The present invention relates to a flame retardant which is a film itself and has an effect of suppressing the supply of air (oxygen) necessary for combustion.

  Since organic materials such as plastic, rubber, wood, and fiber are easily combusted, a flame retardant treatment or a flame proof treatment may be performed using a flame retardant.

Examples of the flame retardant include inorganic types such as antimony trioxide and magnesium hydroxide, phosphorus types such as phosphate ester compounds, and bromine types such as tetrabromobisphenol A.
In addition, powder flame retardants are kneaded into the object to be subjected to flame retardant treatment or flame proof treatment, and liquid flame retardants are impregnated into the object to be flame retardant treated or flame proofed. Used by kneading.

  Patent Document 1 (Japanese Patent Application Laid-Open No. 2003-253123) describes a flame retardant material obtained by treating wood with an aqueous flame retardant treatment composition containing an organosilicon compound, boric acid or phosphoric acid, and water. Has been. The water-based flame retardant treatment composition described in Patent Document 1 contains water as an essential component (claims), does not gel (paragraph number 0059), and does not form a film.

JP 2003-253123 A

  When a flame retardant of a powder is kneaded into a plastic or rubber to impart flame retardancy, the strength of the plastic or rubber often decreases because incompatible powders are mixed in the composition. In addition, when a flame retardant is kneaded into plastic or rubber to impart flame retardancy, the flame retardant contained in the plastic or rubber may act as a plasticizer and may ooze out. May be.

  Further, in order to impregnate wood with a liquid flame retardant, it may take a long processing time or require a large facility.

  The present invention solves the above-mentioned problems, and provides a flame retardant which has an effect of suppressing the supply of air (oxygen) necessary for combustion by itself becoming a coating film.

  The present invention does not require a complex process such as hydrolysis required in the sol-gel method, and is selected from the group consisting of phosphorus compounds as a high-transparency and excellent hard coat property. An object of the present invention is to provide a novel flame retardant comprising at least one kind of compound.

The present invention solves the above problems,
(A) Silane compound containing an amino group represented by the following formula: R _4-n —Si— (OR ′) _n
(Wherein R represents an amino group-containing organic group, R ′ represents a methyl group, an ethyl group or a propyl group, and n represents an integer selected from 1 to 3); and (b) H ₃ BO _At least one boron compound selected from the group consisting of ₃ and B ₂ O ₃ :
(A) a polymer substance containing a reaction product obtained by reacting (b) component at a ratio of 0.02 mol or more with respect to 1 mol of component;
(C) at least one compound selected from the group consisting of phosphorus compounds;
Including flame retardant.

  Furthermore, this invention relates to the coating agent containing the said polymer composition.

  It does not require complicated steps such as hydrolysis required by the sol-gel method, has high weather resistance, excellent optical properties (for example, transparency), and excellent hard coat properties. A flame retardant having an effect of suppressing the supply of air (oxygen) necessary for combustion is obtained. The flame retardant of the present invention can impart flame retardancy to wood, paper, plastic, rubber and the like. For example, by applying the flame retardant of the present invention to paper or cloth, it is possible to obtain a flame retardant sheet without powder falling off.

(Detailed explanation)
Regarding the polymer substance containing the reaction product obtained by reacting the component (a) and the component (b) in the present invention, the inventors have already filed a Japanese patent application on May 31, 2005. (Japanese Patent Application No. 2005-159037), and PCT international application was filed on May 31, 2006 (PCT / JP2006 / 310859). The present application is incorporated into the present application by referring to the contents of these Japanese patent applications and PCT international applications.

  When the component (a) (silane compound containing an amino group) and the component (b) (boron compound) are mixed, they react to form a transparent and viscous liquid in several minutes to several tens of minutes and solidify. This is presumably because the boron compound acts as a crosslinking agent via the amino group in the component (a), polymerizes these components, resulting in a viscous liquid and solidifies. . In addition, (a) component is a liquid. In the present invention, water is not used in the reaction between the component (a) and the component (b).

The component (a) is a silane compound containing an amino group represented by the following formula.
R4 _-n- Si- (OR ') _n
(In the formula, R represents an amino group-containing organic group, R ′ represents a methyl group, an ethyl group or a propyl group, and n represents an integer selected from 1 to 3).

  Here, R represents an amino group-containing organic group. For example, monoaminomethyl, diaminomethyl, triaminomethyl, monoaminoethyl, diaminoethyl, triaminoethyl, tetraaminoethyl, monoaminopropyl, diaminopropyl, Examples include triaminopropyl, tetraaminopropyl, monoaminobutyl, diaminobutyl, triaminobutyl, tetraaminobutyl, and organic groups having an alkyl group or aryl group having more carbon atoms than these. It is not limited. γ-aminopropyl and aminoethylaminopropyl are particularly preferred, and γ-aminopropyl is most preferred.

  R 'in component (a) represents a methyl group, an ethyl group or a propyl group. Among these, a methyl group and an ethyl group are preferable.

In the component (a), n represents an integer selected from 1 to 3. Among them, n is preferably 2 to 3, and n is particularly preferably 3.
That is, as the component (a), γ-aminopropyltriethoxysilane and N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane are particularly preferable.
In the present invention, as the silane compound containing the amino group of the component (a), a hydrolyzed product obtained by previously hydrolyzing the silane compound can also be used.

The component (b) is at least one boron compound selected from the group consisting of H ₃ BO ₃ and B ₂ O ₃ . The component (b) is preferably H ₃ BO ₃ .

The amount of both components used in the reaction between component (a) and component (b) is a ratio of 0.02 mol or more of component (b) to 1 mol of component (a), preferably 0.02 mol. A ratio of ˜8 mol, more preferably a ratio of 0.02 mol to 5 mol.
If the amount of the component (b) is less than 0.02 mol with respect to 1 mol of the component (a), the time required for solidification may become long or may not be sufficiently solidified. Moreover, when (b) component exceeds 8 mol, (b) component may remain without melt | dissolving in (a) component.

  The mixing conditions (temperature, mixing time, mixing method, etc.) of the polymeric substance (a) component and the (b) component of the present invention can be appropriately selected. Under normal room temperature conditions, it becomes a transparent and viscous liquid in several minutes to several tens of minutes, and then solidifies. The time for solidification and the viscosity and rigidity of the reaction product obtained also differ depending on the proportion of the boron compound.

  The boron compound (b) is preferably a boron compound alcohol solution dissolved in an alcohol having 1 to 7 carbon atoms. Examples of the alcohol having 1 to 7 carbon atoms include methyl alcohol, ethyl alcohol, various propyl alcohols, various butyl alcohols, and glycerin, and methyl alcohol, ethyl alcohol, and isopropyl alcohol are preferable. By using the alcohol solution, the time for dissolving the component (b) in the component (a) can be shortened. In view of handling, the concentration of the boron compound in the alcohol is preferably high.

  The reaction product is preferably a reaction product obtained by reacting the component (a) and the component (b) without passing through a step of hydrolysis by adding water.

  The component (c) is at least one compound selected from the group consisting of phosphorus compounds.

  (C) By mix | blending a component, a flame-retardant function is provided to the flame retardant of this invention.

  The component (c) is not particularly limited as long as it is at least one compound selected from the group consisting of phosphorus compounds. (C) As a component, phosphoric acid and its ester can be mentioned, for example.

  The component (c) is preferably added in an amount of 1 to 30 parts by weight, more preferably 2 to 25 parts by weight, based on 100 parts by weight of the component (a) in the flame retardant of the present invention. The flame retardancy depends on the concentration of the component (c), but if the amount of the component (c) is less than 1 part by weight, it may be difficult to show a flame retardant effect, and if it exceeds 30 parts by weight, the flame saturates. It is not preferable in terms of economy.

  Examples of the component (c) include aromatic phosphates such as triphenyl phosphate, tricresyl phosphate, and trixylenyl phosphate, 1,3-phenylene bis (dixylenyl) phosphate, bisphenol A bis (diphenyl phosphate), and the like. Aromatic condensed phosphates, halogen-containing phosphates such as tris (dichloropropyl) phosphate, tris (chloroethyl) phosphate, halogen-containing condensed phosphates such as polyoxyalkylenebisdichloroalkylphosphate, polyphosphoric acid, And red phosphorus.

  It is preferable that the flame retardant of the present invention has pH ≧ 3.

  The flame retardant of the present invention can further contain a metal alkoxide and / or a metal alkoxide condensate as the component (d). That is, the component (d) can be added after the component (c) is added. By adding the component (d), the content of the metal salt in the obtained reaction product can be increased, the chemical characteristics can be further improved, and the same as the case where the component (d) is not used. Since it is in a viscous liquid state, it can be processed into fibers or films.

  Examples of the metal of the metal alkoxide as component (d) include Si, Ta, Nb, Ti, Zr, Al, Ge, B, Na, Ga, Ce, V, Ta, P, and Sb. It is not limited to these. Si, Ti, Zr, and Al are preferable, Si, Ti, and Zr are more preferable. Since the metal alkoxide of the component (d) is preferably liquid, Si and Ti are particularly preferable. Examples of the alkoxide (alkoxy group) of the metal alkoxide of component (d) include methoxy, ethoxy, propoxy, butoxy, and alkoxy groups having more carbon atoms. Methoxy, ethoxy, propoxy, and butoxy are preferred, and methoxy and ethoxy are more preferred.

  Specific examples of the component (d) metal alkoxide include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, ethyltriethoxysilane, propyltripropoxysilane, butyltributoxysilane, tetra Methoxy titanium, tetraethoxy titanium, tetrapropoxy titanium, tetrabutoxy titanium, methyl trimethoxy titanium, ethyl triethoxy titanium, propyl tripropoxy titanium, butyl tributoxy titanium, tetramethoxy zirconium, tetraethoxy zirconium, tetrapropoxy zirconium, tetrabutoxy zirconium , Methyltrimethoxyzirconium, ethyltriethoxyzirconium, propyltripropoxyzirconium, and butyl And the like butoxy zirconium. Among them, preferred are tetraethoxysilane, tetramethoxysilane, ethyltriethoxysilane, and methyltrimethoxysilane, and more preferred are tetraethoxysilane and tetramethoxysilane. .

  (D) The usage-amount of the metal alkoxide of a component has a preferable ratio of 10 mol or less with respect to 1 mol of (a) component. More preferably, it is a ratio of 0.1 mol to 5 mol. If the amount of the component (d) is less than 0.1 mol with respect to 1 mol of the component (a), it may be difficult to obtain the effect of adding the component (d) as described above. Beyond the mole, the curing time can be long.

（式中、Ｒ^１は、アルキル基を表わし、その一部は水素であってもよく、Ｒ^１は、夫々独立に同一であっても異なっていてもよく、ｍは２〜２０から選択される整数を表わし、Ｍは、Ｓｉ、Ｔｉ及びＺｒからなる群から選択される少なくとも１種の金属を表わす。） Examples of the metal alkoxide condensate of component (d) include metal alkoxide condensates (d) represented by at least one formula selected from the group consisting of the following formulas (d1) and (d2). it can.

(In the formula, R ¹ represents an alkyl group, part of which may be hydrogen, R ¹ may be the same or different independently, and m is selected from 2 to 20) M represents at least one metal selected from the group consisting of Si, Ti and Zr.)

  That is, the component (d) can be added during or after the reaction between the component (a) and the component (b). By adding the component (d), the hardness can be increased, the chemical properties can be further improved, and a viscous liquid state can be obtained, so that it can be processed into a fiber or a film.

  The amount of the condensate of the metal alkoxide that is component (d) is preferably 0.1 to 10 mol in terms of the weight of the metal alkoxide monomer with respect to 1 mol of component (a), and is 1 mol or more. More preferably. That is, when the amount of component (d) added is too large, the hardness tends to decrease. On the other hand, when the amount is too small, the Si content decreases, so that the hardness may decrease depending on the application. Durability issues may occur. Moreover, when there is too much addition amount of (d) component, there exists a tendency for the hardening time for obtaining the film of the flame retardant of this invention to become long.

(D) R ¹ in the component represents an alkyl group, part of which may be hydrogen, and R ¹ may be independently the same or different, but R ¹ is a methyl group , An ethyl group, a propyl group, a butyl group, and an alkyl group having a carbon number higher than that, preferably a methyl group or an ethyl group.

  In the component (d), m represents an integer selected from 2 to 20, preferably 3 to 10, and most preferably 5.

  M in the component (d) represents at least one metal selected from the group consisting of Si, Ti and Zr, preferably Si or Ti, and most preferably Si.

  As the metal alkoxide monomer unit constituting the component (d), tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, ethyltriethoxysilane, propyltripropoxysilane, butyltributoxysilane, Tetramethoxytitanium, tetraethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium, methyltrimethoxytitanium, ethyltriethoxytitanium, propyltripropoxytitanium, butyltributoxytitanium, tetramethoxyzirconium, tetraethoxyzirconium, tetrapropoxyzirconium, tetrabutoxy Zirconium, methyltrimethoxyzirconium, ethyltriethoxyzirconium, propyltripropoxyzirconium And a butyl tributoxyzirconium can be exemplified.

  When the component (d) is represented by the formula (d1), it is preferably a tetraethoxysilane condensate (pentamer) or a tetramethoxysilane condensate (pentamer), and the formula (d2 ) Is preferably a condensate of ethyltriethoxysilane (pentamer) or a condensate of methyltrimethoxysilane (pentamer).

  As described above, the flame retardant of the present invention can contain a metal alkoxide (monomer) and / or a metal alkoxide condensate as the component (d), but the viscosity of the metal alkoxide monomer is higher than that of the condensate. Therefore, by further containing a metal alkoxide monomer, there is an advantage that the adhesion of the obtained flame retardant to the substrate may be improved, but the content of the metal alkoxide monomer and the condensate may be reduced. If the amount is increased by the same amount or more, the film property may be deteriorated when the coating film is thickened.

  In addition to the above-listed components, the flame retardant of the present invention is an inorganic filler (calcium carbonate, aluminum hydroxide, magnesium hydroxide, glass fiber, etc.), metal oxide, metal (zinc, aluminum, etc.) depending on its application. Etc.) Powder etc. can be included.

  A coating agent can be obtained by including the flame retardant of the present invention as a main component.

  Since the flame retardant of the present invention can be applied even with a viscosity of 1 poise or less, it can be modified while making use of the material of the base material by impregnating the inside of the base material.

Hereinafter, the present invention will be described in more detail with reference to examples.
The flame retardant having the composition shown in the following examples was prepared by thoroughly mixing the components (a) and (b) at room temperature, and then modifying the reaction, and then adding and stirring the component (c). .
In addition, (b) component was disperse | distributed to isopropanol and it mix | blended it as a 10 weight% isopropanol dispersion liquid.

Example 1
(A) 100 parts by weight of γ-aminopropyltriethoxysilane ((C ₂ H ₅ O) ₃ SiC ₃ H ₆ NH ₂ ) as component, 40 parts by weight of boric acid (H ₃ BO ₃ ) as component (b) As a component (c), 20 parts by weight of phosphoric acid was kneaded and heated to prepare a compound obtained by dealcoholizing aminosilane. By adding 100 parts by weight of water to the obtained compound to form a hydrate, a flame retardant comprising a sol solution containing silanol and containing a large amount of inorganic substances was prepared.
The obtained flame retardant preparation solution was impregnated into filter paper (5C) to form a film, and a flame retardant was adhered to half the weight of the filter paper and subjected to a flameproof test. In the flameproof test, a specimen support frame was mounted at 45 degrees in a combustion test box, and a flame of a burner burned with liquefied petroleum gas as fuel was brought into contact with the specimen.
“Residual flame time” is the time from when the ignition source is removed until the test piece flares up and stops burning. “Residual flame time” refers to the test after the ignition source is removed. This is the time until the piece stops burning without raising flames.
As a result of the flameproof test, the afterflame time and the afterdust time were both 0 seconds.

Example 2
100 parts by weight of an aminosilane hydrolyzed product obtained by hydrolyzing γ-aminopropyltriethoxysilane ((C ₂ H ₅ O) ₃ SiC ₃ H ₆ NH ₂ ) as component (a) and boric acid (H ₃ BO ₃ ) and 40 parts by weight of phosphoric acid as component (c) were kneaded to prepare a flame retardant composed of a viscous sol having a solid content of 70%.
The obtained flame retardant preparation liquid was impregnated into filter paper (5C) to form a film, and a flame retardant was adhered to half the weight of the filter paper and subjected to a flameproof test. As a result of the flameproof test, the afterflame time and the afterdust time were both 0 seconds.
In addition, the flame retardant which consists of a viscous sol liquid prepared in Example 2 can also be used as a flame retardant, after adjusting to a favorite viscosity by diluting with water according to a use.

Example 3
100 parts by weight of an aminosilane hydrolyzed product obtained by hydrolyzing γ-aminopropyltriethoxysilane ((C ₂ H ₅ O) ₃ SiC ₃ H ₆ NH ₂ ) as component (a) and boric acid (H ₃ BO ₃ ) and 40 parts by weight of polyphosphoric acid as component (c) were kneaded and 80 parts by weight of water were added to prepare a flame retardant composed of a viscous sol solution having a solid content of 50%. .
The obtained flame retardant preparation liquid was impregnated into filter paper (5C) to form a film, and a flame retardant was adhered to half the weight of the filter paper and subjected to a flameproof test. As a result of the flameproof test, the afterflame time and the afterdust time were both 0 seconds.

Comparative Example 1
100 parts by weight of an aminosilane hydrolyzed product obtained by hydrolyzing γ-aminopropyltriethoxysilane ((C ₂ H ₅ O) ₃ SiC ₃ H ₆ NH ₂ ) as component (a) and boric acid (H ₃ BO ₃ ) was mixed with 40 parts by weight, and 50 parts by weight of water was added to prepare a flame retardant composed of a viscous sol having a solid content of 50%.
The obtained flame retardant preparation liquid was impregnated into filter paper (5C) to form a film, and a flame retardant was adhered to half the weight of the filter paper and subjected to a flameproof test. As a result of the flameproof test, the afterflame time was 6 seconds and the afterdust time was 10 seconds.

  As described above, as shown in the examples, the object to be treated impregnated with the flame retardant of the present invention has excellent flame retardancy.

  The flame retardant of the present invention can be used as a flame retardant having a coating effect and suppressing the supply of air (oxygen) necessary for combustion.

Claims (5)

(A) Silane compound containing an amino group represented by the following formula: R _4-n —Si— (OR ′) _n
(Wherein, R represents an alkyl group containing an amino group, R 'represents a methyl group, ethyl group or propyl group, n represents an integer selected from 1 to 3); and (b) H ₃ At least one boron compound selected from the group consisting of BO ₃ and B ₂ O ₃ :
(A) a polymer substance containing a reaction product obtained by reacting (b) component at a ratio of 0.02 mol or more with respect to 1 mol of component;
(C) at least one compound selected from the group consisting of phosphorus compounds;
A flame retardant containing ,
(C) A flame retardant wherein the phosphorus compound is phosphoric acid or an ester thereof or polyphosphoric acid .   The flame retardant according to claim 1, wherein a hydrolyzed product obtained by previously hydrolyzing the aminosilane compound (a) is used as the aminosilane compound (a).   The flame retardant according to claim 1, wherein the boron compound (b) is a boron compound alcohol solution dissolved in an alcohol having 1 to 7 carbon atoms.   The flame retardant according to claim 1 or 2, further comprising (d) a metal alkoxide and / or a metal alkoxide condensate. The flame retardant according to claim 4 , wherein the metal in component (d) is at least one element selected from the group consisting of Si, Ti and Zr.