JPH06220224A - Production of cured thin film of phosphazene composition - Google Patents

Abstract

PURPOSE:To obtain a composition suitable for the coating purpose by solving the problem that the melting point becomes higher when an aromatic chain is introduced into a phosphazene derivative and therefore the obtained product is difficultly liquefiable and to provide a process for producing a thin film for a hard coat improved in heat and water resistances. CONSTITUTION:The production process comprises curing a composition, wherein the molecular structure of the principal component is one of a cyclic compound consisting of P=N bonds, the side chain groups on the P atoms constituting its skeleton are derived from a compound selected from an aromatic derivative (A) and an aliphatic derivative (B), and a least 90mol.% component containing both A and B as side chain groups in the same molecule is contained, with ultraviolet rays, electron beams, heat or the like.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a high-hardness film having excellent transparency, heat resistance and flame retardancy, and particularly to easily form a film on the surface of other plastics materials to improve the physical properties. The present invention relates to a high hardness thin film manufacturing method capable of achieving the above.

[0002]

BACKGROUND OF THE INVENTION Generally, a material that forms a film on the surface of a plastic material to increase its hardness is called a hard coat agent,
Materials such as silicone-based, acrylic-based, and titanate-based materials have been developed. These hard coating agents can be roughly classified into organic materials and inorganic materials, but the inorganic materials are superior to the organic materials when attention is paid to the characteristics of high hardness as a function. However, the properties such as toughness and the manufacturing method are inferior to those of organic materials. Therefore, an organic-inorganic hybrid hard coating agent has also been studied for the purpose of overcoming the drawbacks of both.

As organic-inorganic hybrid compounds, 2
About 0 years ago, phosphazene derivatives composed of P = N bonds have been well studied, and a compound obtained by adding allyl alcohol to a cyclic compound derivative of 3 units of P = N units is exposed to ultraviolet rays.
A method of curing using an electron beam or heat is known. However, as is well known, a compound group composed of an aliphatic chain which does not contain a halogen atom and has a poor electron-withdrawing property as a general property of phosphazene derivatives has a problem in water resistance. In order to overcome this drawback, a fluoroalcohol type compound is usually used as an electron-withdrawing side chain group, but introduction of a side chain group of an aromatic compound has been positively studied for economical reasons. However, when an aromatic chain is introduced as a side chain group of phosphazene, the melting point becomes high, and it becomes solid or sherbet-like at room temperature. Therefore, for the purpose of forming a thin film, a large amount of solvent must be used to obtain an appropriate viscosity. In particular, for the purpose of coating, if the raw material before the initiation of polymerization is liquid, good workability and product quality can be obtained.

[0004]

The object of the present invention is to provide a composition which has a high melting point when an aromatic chain is introduced into a phosphazene derivative, improves the properties of a compound that is difficult to be liquid at room temperature, and is good for the purpose of coating. Moreover, it is to provide a method for producing a thin film having improved heat resistance and water resistance.

[0005]

It has been found that the object of the present invention can be achieved by any one of the following constitutions (1) to (6).

(1) The molecular structure of the main component is a cyclic compound composed of P = N bonds, and the side chain group on the P atom forming the skeleton is an aromatic derivative (A) and an aliphatic derivative. A composition which is a compound selected from (B) and which contains 90% or more of the components containing both (A) and (B) as a side chain group in the same molecule in a molar fraction of ultraviolet rays or electron beams. Alternatively, a thin film manufacturing method in which heat or the like is used for curing.

(2) A method for producing a thin film, wherein (A) and / or (B) is composed of a compound having a reactive allyl group and is cured by using ultraviolet rays, electron beams or heat.

(3) Ratio of the number of moles of the above (B) side chain group to the number of moles of the above (A) side chain group (B) /
(A) is a composition whose main component is 0.125-8 (1)
A method for producing a thin film, which comprises curing the cyclic compound derivative composition described in 1. above with ultraviolet rays, electron beams, heat or the like.

(4) The number of P atoms constituting the cyclic skeleton is 3
Is less than 90% in mole fraction, and
In addition, the cyclic compound derivative composition described in (1), which contains as a main component a composition containing 10% or more of a compound component having 4 or more P atoms constituting the cyclic skeleton, is exposed to ultraviolet rays, electron beams, heat or the like. A method for producing a thin film which is cured by using the method.

(5) A method for producing a thin film, wherein the cyclic compound derivative composition described in (1) containing a composition satisfying the above 2 and 3 at the same time as a main component is cured by using ultraviolet rays, electron beams or heat.

(6) The cyclic compound derivative composition described in (1) to (6), wherein a part of the above (A) and / or (B) is a compound exhibiting UV absorption characteristics, such as ultraviolet rays, electron beams or heat. A method for manufacturing a thin film, which comprises curing using.

The present invention will be described in more detail below.

That is, the side chain group on the P atom of the cyclic compound composed of P = N bonds is a compound selected from the aromatic derivative (A) and the aliphatic derivative (B), and (A) and / Or (B) is a compound having a reactive allyl group in the molecule, and contains 90% or more by mole of a compound component having both (A) and (B) as side chains in the same molecule, and The ratio (B) / (A) of the total number of moles of the (B) side chain group and the total number of moles of the (A) side chain group in the composition is in the range of 0.125-8, more preferably in the range of 0.16-6. Or a composition containing 90% or more by mole of a compound component containing both (A) and (B) as a side chain group in the same molecule, and having a cyclic structure. The total of the compound (trimer) components in which the number of P atoms constituting the skeleton of the compound is 3 is 90% or less by mole fraction. And a composition containing 10% or more of a cyclic compound tetramer component having 4 or more P atoms constituting the cyclic skeleton, the hydrolyzability is remarkably improved, and the pour point or melting point is significantly lowered. Synthesized compositions having fluidity at a lower temperature than those composed of similar compounds having an aromatic chain side group, and adding these compositions and a polymerization initiator, etc. A method of manufacturing a thin film which is cured by using is completed.

That is, P = N having only an aliphatic side chain group
By introducing at least one aromatic side chain group into the molecule of a cyclic compound composed of a bond, heat resistance and hydrolysis resistance are significantly improved. On the contrary, by introducing at least one aliphatic side chain group into a compound molecule having only an aromatic side chain group, the fluidity or melting point can be remarkably lowered. If the content of the components containing both side chain groups in one molecule is 90% or less, sufficient heat resistance and hydrolysis resistance may not be obtained, or the pour point or melting point may not be sufficiently lowered. When (B) / (A) is 0.125 or less,
The effect of lowering the pour point or melting point becomes small, and when it is 8 or more, the effect of improving heat resistance and hydrolysis resistance becomes small. Further, when the trimer component is 90% or more, the effect of lowering the pour point or melting point is small, and when the tetramer or more cyclic compound is less than 10%, phenomena such as precipitation of the trimer component occur and stability of the composition May decrease, which is not preferable.

The aromatic side chain group is a group generally derived from a compound having an aromatic ring,

[0016]

[Chemical 1]

A group derived from a compound having a hydroxyl group as a functional group in an aromatic ring such as, or

[0018]

[Chemical 2]

Groups derived from compounds having an amino group as a functional group in the aromatic ring such as An aliphatic chain containing an allyl group may be bonded to these aromatic rings. Further, the combination of the side chain groups of the phosphonitrile ring does not necessarily have to be composed of a single group, and may be a combination selected from a plurality of these groups. Considering heat resistance, hydrolysis resistance and the like, it is preferably selected from a group derived from a compound having a hydroxyl group. The aliphatic side chain group is a group derived from an aliphatic alcohol, an aliphatic amine or the like having a reactive functional group. Among these, a group derived from an aliphatic allyl alcohol is preferable for increasing hardness. Further, it is preferable that the aliphatic side chain group contains a halogen atom in view of the stability of the side chain group. Among the halogen atoms, fluorine is particularly preferable.

Regarding a typical synthesis method of the compound having both the aromatic organic compound and the aliphatic organic compound in the side chains, a mixture of a trimer, a tetramer and an n-mer compound containing a halogen atom is used. , For example, C ₆ H ₅ ONa, CH ₃ C ₆ H ₄ O
The halogen atom can be substituted by using a reagent in which two or more kinds of nucleophiles such as Na and CF ₃ CH ₂ ONa are mixed in an appropriate ratio.

That is, (PNF ₂ ) ₃ , (PNF ₂ ) ₄ ,
(PNCl ₂ ) n (n <15), etc., where the side chain group is a F atom trimer, tetramer, n-mer compound, (PNCl ₂ ) ₃ , (PN
Cl ₂ ) ₄ and (PNCl ₂ ) n (n <15) have side chains of C
l-atom trimer, tetramer, n-mer compound, (PNBr
₂ ) ₃ , (PNBr ₂ ) ₄ , (PNBr ₂ ) n (n <15)
Such as trimeric, tetrameric, n-meric compounds having a side chain group of Br atom, (PNI ₂ ) ₃ , (PNI ₂ ) ₄ , (PNI ₂ ) n (n
The halogen atom of a trimer, tetramer or n-mer compound having a side chain group such as <15) of I atom is replaced with C ₆ H ₅ ONa, CH ₃ C ₆ H ₄
Reaction of aromatic organic compounds such as ONa, (C ₆ H ₅ O) ₂ Ca and CF ₃ CH ₂ ONa with metal salts, aromatic compounds having a hydroxyl group such as C ₆ H ₅ OH or CH ₂ (C
_{H 3) CC (O) O} (CH 2) fatty alcohols, C ₆ H ₅ aromatic and halogen and nucleophilic substitution on P atoms such as amines such as NH _2, such as ₂ -OH And aromatic amine compounds such as aniline, and chlorine acceptor compounds such as sodium hydroxide and sodium carbonate.

The phosphazene derivative used in the present invention is generally synthesized in this manner, but the synthetic method mainly comprising the substitution reaction is not particularly limited. Regarding the method for preparing a mixture containing 90% or less of a phosphazene derivative in which the number of P contained in the cyclic skeleton is 3, the composition of the halogenated phosphazene, which is the raw material before the substitution reaction, is changed to the desired composition. After that, a substitution reaction is performed to obtain an oily substance,
Alternatively, a method may be considered in which after the substitution reaction, a mixture of two or more compositions is mixed to obtain an oily substance, and the like, but the present invention can achieve the object by any method. Considering that the method for synthesizing a single cyclic compound in the synthesis of a halogenated phosphazene is generally difficult and not economical, it is preferable to select a method in which the composition before the substitution reaction is close to an oily substance.

The method for forming a thin film using the phosphazene derivative of the present invention is, for example, a solution in which a solvent such as benzene or toluene is dissolved at an arbitrary ratio and a polymerization initiator and, if necessary, other additives are added. After adjusting and forming a thin film by spin coating or the like, it is cured by using ultraviolet rays, electron beams or heat.

With respect to the polymerization initiator, known polymerization initiators such as those used in the polymerization of compounds having an allyl group can be used, that is, the polymerization initiator suitable for the composition of the present invention can be used by applying energy. A compound that releases or generates free radicals when released. Initiators of this type include the peroxy, azo and redox systems, all of which are well known and are described, for example, in Calvert and Pitts, published by John Wiley & Sons in 1966, in Photo-ch.
It is often described in the technical field of polymerization, including the description in chapter 2 of "emistry". Included among free radical initiators are conventional heat activated initiators such as organic peroxides and organic hydroperoxides, examples of which are:
Benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, azobis (isobutyronitrile)
Etc. A preferred initiator is a photopolymerization initiator that accelerates the polymerization when the composition is irradiated. Initiators of this type include acryloin and its derivatives such as benzoin, benzointyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and α-methylbenzoin; diketones such as benzyl and diacetyl and others; organic sulfides, For example, diphenyl monosulfide, diphenyl disulfide, decyl phenyl sulfide and tetramethyl thiuram monosulfide; S-acyl dithiocarbamates such as S-benzoyl-N, N-dimethyldithiocarbamate; phenones such as acetophenone, α, α,
α-tribromoacetophenone, α, α-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, o-nitro-α, α, α-tribromoacetophenone, benzophenone and p, p'-tetramethyldiaminobenzophenone Salts of aromatic iodonium and aromatic sulfonium; sulfonyl halides such as p-toluenesulfonyl chloride, 1-naphthalenesulfonyl chloride, 2-naphthanesulfonyl chloride, 1,3-benzenedisulfonyl chloride, 2,4-dinitrobenzene Included are sulfonyl bromides and p-acetamidobenzenesulfonyl chloride. The standard amount of initiator used is in the range of about 0.01 to 5% by weight, based on the total weight of the polymerizable composition. When the amount is less than 0.01% by weight, the weight speed is extremely reduced. Even if the amount of the initiator used exceeds 5% by weight, the corresponding improvement in the effect cannot be expected. Therefore, such mass use is not economically feasible. About 0.25
It is desirable to use ˜1.0% of initiator in the weight composition.

For other additives, mention may be made of surfactants such as silicon surfactants.

Regarding the method for forming a thin film, a method of diluting a compound in a solvent and then coating and drying it is used, or a method of coating and drying an aqueous solution in the form of an emulsion may be used.

The composition of the present invention has greatly improved the heat resistance and hydrolysis resistance, which are the drawbacks of the conventionally known phosphazene coating agents, and has the excellent flame retardancy characteristic of the phosphazene coating agents. Properties, excellent electrical insulation and lubricity, and low toxicity, it is widely and suitably applied to coating agents for improving flame retardancy such as resins.

[0028]

EXAMPLES Next, reference examples, examples and comparative examples will be described, but the present invention is not limited thereto. Further, the synthesis reaction was performed under dry nitrogen gas unless otherwise specified.

1. Synthetic Method of Chlorophosphazene Cyclic Compound (Reference Example 1) Hajime Saito, Naruyuki Kajiwara, Engineering, 66,618 (196
3) Add a large excess of NH ₄ Cl to a solution of PCl ₅ dissolved in tetrachloroethane and heat to 130 ° C. or higher. After completion of the reaction, the reaction solution is filtered to separate unreacted NH ₄ Cl.
After distilling the filtrate, the residue is treated with hexane to obtain a mixture of phosphazene cyclic compounds.

Example 1 Pyridine 20 g, phenol 8.9
3 g and 11.22 g of allyl alcohol are dissolved and mixed in THF, and the THF solution containing 10 g of chlorophosphazene obtained in Reference Example 1 is slowly dropped therein. After the dropping is completed, the temperature is heated to a temperature near the boiling point of THF and refluxed for 12 hours. After completion of the reaction, THF is distilled off and the residue is washed with ether and a dilute aqueous solution of sodium hydroxide. After washing, ether extraction is performed, and the ether solution containing the phosphazene derivative is dried with calcium chloride. An oily compound is obtained by removing the ether after drying for one day.

Comparative Example 1 The phosphazene cyclic compound obtained in Reference Example 1 was purified by vacuum distillation (distillation conditions: 120 ° C./10 mmHg). When the compound obtained by distillation purification was analyzed by gas chromatography, 95% or more of the trimer was contained.
Moreover, it was confirmed by ³¹ P-NMR that a compound of a pentamer or more was not contained. This compound is replaced with chlorine only by a phenoxy group by the same reaction as in Example 1. The obtained compound was a solid at room temperature. The melting point was 106 ° C.

Comparative Example 2 Phosphazene distilled and purified in the same manner as in Comparative Example 1 was reacted with the mixed alkoxide in the same manner as in Example 1. The obtained compound was a solid at room temperature. No clear melting point was observed, and it became more than grease at 60 ° C or higher.

The results of Example 1, Comparative Example 1 and Comparative Example 2 are shown in Table 1 above.

[0034]

[Table 1]

From Table 1, it can be seen that if the composition of the cyclic compound composed of P = N bonds is outside the scope of the claims, it will not become a liquid at room temperature.

Example 2 Next, 2 g of the composition obtained in Example 1 was diluted with 4 g of benzene and coated on an aluminum metal plate with a spin coater. When the surface was observed by repeating drying and coating 20 times, it was found that the composition liquid of Example was uniformly applied.

(Comparative Example 3) Composition 2 obtained in Comparative Example 1
After being diluted with 4 g of benzene, coating is performed on an aluminum metal plate with a spin coater. When the surface was observed by repeating drying and coating 20 times, the composition of Comparative Example 1 was applied in a powder form.

From Example 2 and Comparative Example 3, it can be seen that when the composition is liquid and has fluidity, good coating results are obtained.

[0039]

According to the present invention, when an aromatic chain is introduced into a phosphazene derivative, the melting point becomes high, the properties of the compound which is conventionally difficult to be liquid at room temperature are improved, and a composition good for the purpose of coating is provided, Moreover, it is possible to provide a method for producing a thin film having improved heat resistance and water resistance.

Claims (6)

[Claims] 1. A molecular structure of a main component thereof is a cyclic compound composed of P═N bonds, and a side chain group on a P atom forming the skeleton is an aromatic derivative (A) and an aliphatic derivative ( A composition which is a compound selected from B) and contains 90% or more of the components containing both (A) and (B) as a side chain group in the same molecule in a mole fraction of ultraviolet rays, electron beams or A method for manufacturing a thin film that is cured by using heat or the like. 2. A method for producing a thin film, wherein (A) and / or (B) is composed of a compound having a reactive allyl group and is cured by using ultraviolet rays, electron beams or heat. 3. The ratio (B) / (A) of the number of moles of the (B) side chain group and the number of moles of the (A) side chain group as a whole of the composition is
A method for producing a thin film, which comprises curing the cyclic compound derivative composition according to claim 1, which comprises a composition of 0.125-8 as a main component, using ultraviolet rays, electron beams or heat. 4. A compound component in which the total of the compound components in which the number of P atoms constituting the cyclic skeleton is 3 is less than 90% in mole fraction, and the number of P atoms in the cyclic skeleton is 4 or more.
A method for producing a thin film, comprising curing the cyclic compound derivative composition according to claim 1, which comprises a composition containing 10% or more as a main component, using ultraviolet rays, electron beams or heat. 5. A method for producing a thin film, comprising curing the cyclic compound derivative composition according to claim 1, which comprises a composition satisfying both claims 2 and 3 as a main component, using ultraviolet rays, electron beams or heat. 6. A part of (A) and / or (B) is U.
7. A method for producing a thin film, which comprises curing the cyclic compound derivative composition according to claim 1 which is a compound exhibiting V absorption characteristics by using ultraviolet rays, electron beams or heat.