JPH0286694A - Heatproofing agent and flameproofing agent composition - Google Patents

Abstract

PURPOSE:To obtain the title composition which, when applied to paper, can impart thereto improved discoloration resistance upon being heated and improved tearing strength by reacting a specified compound with an alkylene oxide and formaldehyde. CONSTITUTION:A heatproofing agent for a flameproofing agent is obtained by reacting a compound selected from among a dicyandiamide, a urea and a melamine with 1-50wt.% 2-4C alkylene oxide (e.g., propylene oxide) and 0.1-60wt.% formaldehyde (e.g., formalin) at 30-90 deg.C for 1-5hr. A flameproofing agent composition is obtained by mixing 1-99wt.% heatproofing agent with 99-1wt.% guanidine salt selected from among guanidine sulfamate, guanidine sulfate, guanidine borate and guanidine phosphate. An aqueous solution formed by dissolving 0.5-60wt.% this composition in water is applied to a cellulosic material (e.g., paper) and dried to adhere 2-40wt.% said composition to the substrate.

Description

[Detailed description of the invention] [Industrial application fields] The present invention relates to a heat resistant agent and a flame retardant composition.

[Prior Art] Conventionally, dicyandiamide, urea, and melamine have been used as heat-resistant agents for flame retardants. In addition, flame retardants include guanidine sulfamate and methylolated guanidine sulfamate.

[Problems to be Solved by the Invention] However, this product does not have sufficient heat resistance, and when it is applied to paper and heated, the paper tends to become colored, and the tear strength after heating is significantly reduced. There was a point.

[Means for Solving the Problems] The present inventors have found that the quality is sufficient and, for example, when applied to paper and heated, it is difficult to cause paper cracking, and there is little decrease in tear strength after heating. As a result of studies aimed at obtaining a flame retardant composition, the present invention was achieved.

That is, the present invention provides a compound selected from the group consisting of (+) dianediamides, ureas, and melamines, and (2)
A heat-resistant agent for flame retardant consisting of a reaction product of alkylene oxide and (3) formaldehyde, and a heat-resistant agent according to νI requirement l selected from the group consisting of guanidine sulfamate, guanidine sulfate, guanidine borate, and guanidine phosphate. This is a flame retardant composition containing guanidine jp.

In the present invention, the reaction product may be one obtained by reacting formaldehyde with an alkylene oxide C (hereinafter abbreviated as AO) adduct of a compound selected from JjY consisting of dicyandiamides, ureas, and melamines, and dicyandiamides, A to the formaldehyde reaction product of a compound selected from the group consisting of ureas and melamines.
It may also be one with O added thereto.

Examples of dicyandiamide 1 include dicyandiamide, monomethylol dicyandiamide, dimethylol dicyandiamide, etc. Dicyandiamide is preferred.

Examples of ureas include urea, thiourea, guanylurea, guanylthiourea, 2-1 derivatives thereof (biuret, etc.), and medilolated products thereof (monomethylolurea, monomethylolthiourea, etc.). Preferably it is urea.

Melamines include melamine, di- or tetramethylolmelamine, mono- or di-methylol-di- or monotrimethoxymethylmelamine, and the like.

Preferably it is melamine.

In the present invention, the AO used has 2 to 4 carbon atoms.
AO such as ethylene oxide (hereinafter abbreviated as EO),
Propylene oxide (hereinafter abbreviated as PO), l.

One or more of 2-butylene oxide and the like and phenyl or halo substituted products thereof such as styrene oxide, epichlorohydrin, etc. can be used.

Preferred are EO and PO.

When using two or more types of AO, the addition format may be block, random, or a mixture of these.

The amount of AO added is usually 1 based on the weight of the addition reaction starting material.
-70%, preferably 1-50%. Addition amount is 1%
If there are no drops, the tear strength decreases, and if it exceeds 70%, the flame retardance itself may decrease.

The content of AO is usually 1 to 50%, preferably 1 to 45% based on mm in the formaldehyde-reacted product of the AO adduct or the AO adduct of the formaldehyde reactant (hereinafter referred to as the reaction product in the present invention). %.

AO adducts of compounds selected from the group consisting of dicyandiamides, ureas and melamines and AO adducts of formaldehyde-reacted compounds of compounds selected from the group consisting of dicyandiamides, ureas and melamines can be produced by conventional methods. .

For example, a formaldehyde reaction product of a compound selected from 11t consisting of ginandiamides, ureas and melamines or a compound selected from the group consisting of ginandiamides, ureas and melamines is added in a molten state or with water. Using a organic solvent (ketones, alcohols, etc.) as a solvent or dispersion medium, AO without a catalyst or in the presence of a basic catalyst (caustic potash, trimethylamine, etc.) or an acid catalyst (boron trifluoride, etc.) under pressure or normal pressure, 50
It can be manufactured by adding 1 at ~180''C.

Formaldehyde includes formalin (a 37% aqueous solution of formaldehyde) and formaldehyde generating substances such as paraformaldehyde. Formalin is preferred.

The formaldehyde reaction n1 is usually 0.1 to 60%, preferably 0.5 to 50% based on the weight of the reaction starting materials.
It is. Reaction 51 is 0. If it is less than IOA, heat resistance will decrease, and if it exceeds 60%, flame retardancy itself may decrease.

Further, the content of formaldehyde in the reaction product of the present invention is usually 0.1 to 50%, preferably 0.5 to 45%, based on weight.

Formaldehyde reaction product of a compound selected from 11F consisting of dicyandiamides, ureas and melamines,
and 1! consisting of dicyandiamides, ureas and melamines! The formaldehyde reaction product of the AO adduct of the compound selected from Y can be produced by a conventional method.

For example, adding an AO adduct of a compound selected from the group consisting of dicyandiamides, ureas and melamines or a compound selected from the group consisting of dicyandiamides, ureas and melamines to a formaldehyde aqueous solution,
It can be produced by reacting usually at 30 to 90°C for 1 to 5 hours.

Examples of reaction products in the present invention include formaldehyde reaction product of urea-EO adduct (EO content 20%, formaldehyde content 10%), formaldehyde reaction product of non-andiamide EO adduct (EO content [30%, formaldehyde content 1110%]). %), formaldehyde reaction product of PO adduct of melamine (Poffi 20%, formaldehyde content 15%), EO adduct of formaldehyde reaction product of dicyandiamide (EO content 20%, formaldehy 1! 110%), dicyandiamide EO/PO
Formaldehyde reaction product of adduct (EO content 15%, P
Examples include formaldehyde reaction product of dicyandiamide EO/PO adduct (15% EO, 15% PO, filO% formaldehyde).

In the above, the EO/r'o adduct refers to a random adduct of EO and PO, and the EO/PO adduct refers to a block addition of EOlPO in the order. Below, similar notes fill
Use.

The heat resistant agent (A) is used together with a guanidine salt (B) selected from the group consisting of guanidine sulfamate, guanidine sulfate, guanidine borate, and guanidine phosphate to form a flame retardant composition (hereinafter abbreviated as the composition of the present invention). ) can be obtained.

In addition, other guanidine salt compounds (C), such as guanidine salts (guanidine hypophosphite, guanidine polyphosphate, etc.), hydroxyalkyl-substituted guanidine (methylolated guanidine sulfamate, etc.), cyano-substituted guanidine (guanylurea phosphate, guanylurea polyphosphate, etc.), amine-substituted or amine group-containing substituted guanidine salts (aminganidine phosphate, etc.) may be used in combination.

Furthermore, acid ammonium salts (D) (ammonium sulfamate, ammonium sulfate, ammonium phosphate, etc.), dicyandiamides (E) (dicyandiamide, methylolated dicyandiamide, etc.), ureas (F) (urea, thiourea, guanylurea) etc.), melamines (G) (melamine, methylolated melamine, etc.) may be used in combination.

The compositions of the present invention typically include (A), (B), (C), (D
), (E), (F), (G), etc. can be mixed.

In the composition of the present invention, the content of the heat resistant agent (A) is usually 1 to 99% by weight, preferably 1 to 70% by weight.
%. If tS is less than 1%, the performance as a heat resistance agent will not be sufficiently exhibited, and if it exceeds 99%, the flame retardancy itself will decrease.

The use of guanidine salt (1']) is usually 1-99%, preferably 30-! ]0%, particularly preferably 50-99
%.

Component (C) is usually 0 to 70%, preferably 0 to 50%. (D), (E), (F) Rice (G) component is usually 0 to 70%, preferably 0 to 50%.

Preferably, it is used as the Allll mature tree solution of the present invention. When dissolved, the concentration can be varied depending on the purpose of use, but the concentration used is usually 0.5 to 60%, preferably 1 to 50% in terms of solid content of the composition.

Substrates to which the composition of the present invention can be used include cellulosic materials such as paper (shoji paper, fusuma paper, wallpaper, paperboard, synthetic paper, etc.). It can also be used for fiber materials such as cloth, and building materials such as wood, plywood, and synthetic wood.

The amount of the composition of the present invention deposited on the substrate is usually 2 to 40%, preferably 3 to 35% in terms of solid content.

The composition of the present invention can be applied to a substrate using conventional methods, such as immersing paper in the composition of the present invention or its water diluted solution and drying it, or using a size press. There are methods such as applying it, applying it with a brush, etc.

Further, the composition of the present invention can be used in combination with a sizing agent, a surface treatment agent such as starch, and other low treatment agents.

[Example] The present invention will be further explained below with reference to Examples, but the present invention is not limited thereto. Parts in Examples and Comparative Examples indicate parts by weight.

Example 1 114 parts of dicyandiamide was dissolved and dispersed in 75 parts of water, and P
Add 2 parts of O2 under pressure and 90~! The reaction was carried out at 30°C for 6 hours to obtain an AO adduct with an EO content of 16%.

41 parts of formalin was added to this, and the mixture was reacted for 2 hours at 40 to BO°C to obtain a reaction product (heat resistant agent) with a solid content of about 60%.

Example 2 Dissolve and disperse 60 parts of urea in 37 parts of water and add 20 parts of PO under pressure! ]O to 130°C for 6 hours to obtain an AO adduct with a PO content of 25%. Thereafter, in the same manner as in Example 1, a reaction product (heat resistant agent) having a solid content of approximately 60% was obtained.

Example 3 126 parts of melamine was dissolved and dispersed in 88 parts of water to form EO and PO.
30 parts of a mixture (EO/PO = 3/1 weight ratio) was added under pressure and reacted at 90 to 130°C for 6 hours to obtain an AO adduct with an AO content of 19% in the adduct. Below, Example 1
In the same manner as above, a reaction product with a solid content of about 60% (heat resistant agent)
was gotten.

Example 4 40 parts of the reaction product of Example 1, 460 parts of guanidine sulfamate, and 500 parts of water were mixed and stirred at 50 to 70°C for 1 hour to obtain a flame retardant composition.

Example 5 40 parts of the reaction product of Example 2, 460 parts of guanidine sulfamate and 500 parts of water were added and heated at 50 to 70°C.
A flame retardant composition was obtained by stirring for a period of time.

Example 6 40 parts of the reaction product of Example 3, 460 parts of guanidine sulfamate and 500 parts of water were added and heated at 50 to 70'C.
A flame retardant composition was obtained by stirring for a period of time.

Example 7 114 parts of dicyandiamide was dissolved and dispersed in 73 parts of water, 41 parts of formalin was added, and the mixture was reacted at 40 to 60"C.
Add 20 parts of EO under pressure and react at OO~+30'C for 6 hours to add EO to give a reaction product of about 60% solid (
heat resistant agent) was obtained.

To 40 parts of this reaction product, 4 GO parts of guanidine sulfamate and 500 parts of water were added and heated at 60 to 80°C for 1 hour.
A flame retardant composition was obtained by stirring for a period of time.

Comparative Example 1 100 parts of methylolated guanidine sulfamate, 400 parts of guanidine sulfamate, and 500 parts of water were mixed and stirred at 50 to 70°C for 60 minutes to obtain a flame retardant composition.

Comparative Example 2 400 parts of guanidine sulfamate and 600 parts of water were mixed to obtain a flame retardant composition.

Comparative Example 3 100 parts of methylolated guanidine sulfamate, 360 parts of guanidine sulfamate, 40 parts of dicyandiamide
and 500 parts of water were mixed and stirred at 50 to 70°C for 60 minutes to obtain a flame retardant composition.

Comparative Example 4 100 parts of methylolated guanidine sulfamate, 360 parts of guanidine sulfamate, 40 parts of urea, and 5 parts of water.
00 parts were mixed and stirred at 50 to 70°C for 60 minutes to obtain a flame retardant composition.

Test Example 1 Using the flame retardant compositions of Examples 4 to 7 and Comparative Examples 1 to 4, paper was treated with the treatment liquid by the size press method to
+05°C/! After keeping it dry in an auto dryer, performance was evaluated using the following method. The results are shown in Table-1.

Coloration prevention property: Heated in an oven at 180°C for 10 minutes and compared the degree of coloration.

Tear strength: Immediately after heating the sample in an oven at 180° C. for 0 minutes, it was measured according to the JIS-P-811 tear strength test method for paper.

Flame retardancy: The carbonizing tool was measured in accordance with JIS-Z-215Or "Flame retardant test for thin materials" (456 Metzkel burner method).

Table-1 Anti-coloring property ○: light yellow, △: yellow, ×: light brown Flame retardant: carbonizing tool (mm) [Effects of the invention] The composition of the present invention is different from conventional compositions (for example, dicyandiamide as a heat resistant agent) It has improved heat resistance compared to those (containing 1), and in particular has further improved premature color resistance and tear strength when applied to paper and heated.

Furthermore, when used as a water-soluble material, it is easy to dissolve and has good compatibility with other processing agents, such as sizing agents and binders (starch, polyvinyl alcohol), so it dissolves quickly and has good workability.

Because it has the above effects, the composition of the present invention can be used for paper, cloth,
It is effective for many applications such as wood and building materials.

Claims (1)

[Scope of Claims] 1. A heat resistant agent for flame retardants comprising a reaction product of (1) a compound selected from the group consisting of dicyandiamides, ureas, and melamines, (2) alkylene oxide, and (3) formaldehyde. . 2. A flame retardant composition comprising the heat resistant agent according to claim 1 and a guanidine salt selected from the group consisting of guanidine sulfamate, guanidine sulfate, guanidine borate, and guanidine phosphate.