JPH061869A - Member coated with phosphazene resin - Google Patents

Abstract

PURPOSE:To obtain the title member having improved weatherability and abrasion resistance by forming on a substrate an intermediate layer of a curable or thermoplastic resin having specified properties and forming on the intermediate layer a surface layer of a curable phosphazene resin. CONSTITUTION:The title member is produced by forming on a substrate an intermediate layer of a curable resin having a thermal expansion coefficient (at 40 deg.C) higher than 5X10<-5>cm/cm. deg.C or a thermoplastic resin having a tensile modulus lower than 2,000 MPa and forming on the intermediate layer a surface layer of a curable phosphazene resin. A thermosetting resin (e.g. a phenol resin or an unsatd. polyester resin) or a photocurable resin [e. g. a photopolymn. product of a polyfunctional (meth)acrylic ester] is used as the curable resin; examples of the thermoplastic resin are an acrylic resin, a polyurethane resin, and a polycarbonate resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a phosphazene resin coated member, and more particularly to a phosphazene resin coated member having improved weather resistance and abrasion resistance.

[0002]

2. Description of the Related Art A technique for producing a resin-coated member by coating and curing a photopolymerizable resin composition comprising a photopolymerizable compound, a photopolymerization initiator, an ultraviolet absorber, etc. is known. For example, it is disclosed in Japanese Patent Application Laid-Open No. 2-261831. According to these techniques, the weather resistance and the abrasion resistance can be improved by coating the photopolymerizable resin composition and providing the cured resin surface layer. However, compared with, for example, a silicone-based hard coating material, the weather resistance and abrasion resistance are still unsatisfactory from a practical level, and it cannot be denied that the performance is slightly inferior. Among these, the phosphazene-based cured resin layer containing a curable phosphazene-based compound as a main component,
For example, as disclosed in Japanese Unexamined Patent Publication No. 63-241075, it has excellent mechanical properties such as surface hardness and heat resistance, and is widely used as various coating materials, protective film forming materials and the like. However, the phosphazene-based cured resin coating layer has a smaller coefficient of thermal expansion than the base material made of a thermoplastic resin or the like. There is a problem that peeling easily occurs between the two.

[0003]

Therefore, the present inventors have
In view of the above situation, the inventors have conducted intensive studies to solve the drawbacks of the conventional method and to develop a phosphazene resin-coated member having excellent quality. As a result, a curable resin having a coefficient of thermal expansion at 40 ° C. of more than 5 × 10 ⁻⁵ cm · cm ⁻¹ · ° C. ⁻¹ or a thermoplastic resin having a tensile elastic modulus of less than 2,000 MPa is formed on the substrate. It has been found that by providing the intermediate layer, a phosphazene-based resin coated member having desired properties can be obtained. The present invention has been completed based on such findings. That is, according to the present invention, the substrate and the thermal expansion coefficient at 40 ° C. provided on the substrate are 5 × 10 5.
Provided is a phosphazene-based resin coated member comprising an intermediate layer of a curable resin having a size of greater than ^-5 cm · cm ⁻¹ · ° C. ⁻¹ and a surface layer of a phosphazene-based cured resin provided on the intermediate layer. To do. Further, the present invention comprises a substrate, an intermediate layer of a thermoplastic resin having a tensile elastic modulus of less than 2,000 MPa provided on the substrate, and a surface layer of a phosphazene-based cured resin provided on the intermediate layer. Also provided is a phosphazene-based resin coating member characterized by:

First, in the present invention, various substrates can be used. For example, as plastics, regardless of whether they are thermoplastic or thermosetting, various plastics such as polycarbonate, polymethylmethacrylate, polyallyldiglycolcarbonate, polystyrene, acrylonitrile-styrene copolymer (A
S), polyvinyl chloride, acrylonitrile-butadiene-styrene copolymer (ABS), polyester and the like. These are plate-shaped, sheet-shaped, film-shaped, rod-shaped, etc., and their shapes are not particularly limited. Of these, a substrate made of polycarbonate or polymethylmethacrylate is often used by taking advantage of its optical properties, heat resistance, impact strength, and the like, and especially from the viewpoint of wear resistance. It is preferably used.
In addition, as the substrate, wood, metal, ceramics, or a composite material, for example, ships such as ships and skis in fiber reinforced resin (FRP), and carbon reinforced resin (CRP)
There are tennis rackets and golf shafts.

In the present invention, on such a substrate,
Prior to providing the surface layer of phosphazene-based cured resin
Is a curable resin or thermoplastic resin having specific properties.
An intermediate layer made of fat is provided.
It These curable or thermoplastic resins are
They may be used alone or in combination. here
And the curable resin used to provide the intermediate layer on the substrate
Is made of thermosetting resin or photocurable resin.
is there. These thermosetting resins or photocurable resins are
Both have a thermal expansion coefficient of 5 x 10 at 40 ° C.^-Fivecm
·cm^-1・ ℃ ^-1Have greater properties than. Such special
Among the curable resins having properties, as the thermosetting resin,
There are various types. Specifically, for example, phenol tree
Fat, melamine-formaldehyde resin, urea-formua
Ludehide resin, epoxy resin, unsaturated polyester resin
Examples include fats and polyurethane resins.

The photocurable resin is, for example, one obtained by photopolymerizing a polyfunctional (meth) acrylic acid ester monomer or an oligomer thereof. This polyfunctional (meth) acrylic acid ester monomer has the general formula (I) or (I ′)

[0007]

[Chemical 1]

It is represented by Here, n is an integer of 2 to 8, preferably 2 to 6, particularly preferably 2 to 4, and R
¹ represents an n-valent alkyl group, substituted alkyl group, ether or polyether group, substituted ether or polyether group, alkenyl group, substituted alkenyl group, aryl group, substituted aryl group, alkaryl group or aralkyl group, and here The expressions "n-valent alkyl group, alkenyl group and aryl group" used in Section 1 above mean n-valent aliphatic saturated hydrocarbon group, aliphatic unsaturated hydrocarbon group and aromatic hydrocarbon group, respectively. Preferred alkyl groups for R ¹ are those having 1-20 carbon atoms. Examples of suitable alkyl groups include methyl, ethyl,
n-propyl, isopropyl, n-butyl, isobutyl, pentyl, isopentyl; 2,2,4-trimethylpenter, neopentyl, pentyl, trimethylpropyl, hexyl, octyl, nonyl and the like. The unsubstituted alkyl group is preferable, but a substituted alkyl group can also be used. Alkyl is halogen, such as fluorine, chlorine,
Bromine and iodine, hydroxyl, -COOR 'group and -OR' group (in the formula, R'represents an alkyl group having 1 to 6 carbon atoms), -OH group, -COOH group and -NO.
_It can be substituted with a substituent such as _two groups. Examples of this substituted alkyl include n-propyl chloride, isopropyl chloride, t-butyl bromide; 1-bromo-2,2-dimethylpropyl; 1-chloro-2-hydroxy-3-methylbutyl;
1,4-dichloro-2-methylbutyl; ethylenechlorohydrin; 3-methyl-2-hydroxybutyl; 2,4
-Dihydroxypentyl; acetonitrile, t-butyl hydroxide and the like.

Preferred alkenyl groups are alkenyl groups having 2 to 20 carbon atoms. Examples of suitable alkenyl groups include ethylene, propylene, isobutylene, 2
-Butene, 2-pentene, 3-hexene, 3-heptene, 3-methyl-2-butene; 3,3-dimethyl-2-
Butene; 4,4-dimethyl-2-hexene; 2,4,4
-Trimethyl-2-pentene and the like. The alkenyl group is preferably an unsubstituted alkenyl group, but the substituted alkenyl group is, for example, 4-chloro-2-pentene, 4-hydroxy-2-pentene, 2-chloro-3-hydroxy-1.
-Propylene, 3-bromo-1-propylene and the like can also be used. Suitable ether groups are those having 2 to 20 carbon atoms. Examples of ether groups include dimethyl ether, diethyl ether, dipropyl ether, methyl ethyl ether, ethyl propyl ether, diisobutyl ether, propyl isobutyl ether and the like. Suitable polyether groups contain 5 to 20 carbon atoms and have the general formula (II)

[0010]

[Chemical 2]

(In the formula, R ² represents a substituted alkylene group,
x is an integer of 2-5. ) Has. Unsubstituted ethers and polyethers are preferred, but substituted ethers and polyethers can also be used. Suitable aryl groups are 6 to
Those having 12 carbon atoms, namely phenyl, naphthyl and anthryl. Unsubstituted aryl groups are preferred, but substituted aryl groups can also be used. Substituted aryl groups are those containing 6 to 12 carbon atoms and 1 to 6 substituents. Examples of the substituted aryl group include bromophenyl; 1,5-dibromophenyl; nitrophenyl; 1-hydroxy-4-bromophenyl and the like.
Suitable alkaryl and aralkyl groups are those having 7 to 20 carbon atoms. Examples of the alkaryl and aralkyl groups include tolyl, ethylphenyl, n
-Ethyltolyl, xylyl, 2-phenylpropyl, 1
-Such as phenylbutyl. If a substituent is present,
It should be noted that these do not significantly interfere with or suppress the photocuring of the polyfunctional acrylic acid ester monomers.

This polyfunctional acrylic acid ester monomer is specifically, for example, a difunctional acrylic acid ester monomer in which n is 2 in the formula (I), that is, a diacrylate,

[0013]

[Chemical 3]

[0014]

[Chemical 4]

Examples include compounds represented by: Further, in the formula (I), as the trifunctional acrylic acid ester monomer in which n is 3, that is, triacrylate,
For example, the expression

[0016]

[Chemical 5]

Examples thereof include compounds represented by Further, in the formula (I), as the tetrafunctional acrylic acid ester monomer in which n is 4, that is, tetraacrylate, for example,

[0018]

[Chemical 6]

Compounds such as These polyacrylic acid esters and their production methods are well known to those skilled in the art. As an example of a method for producing di-, tri- and tetraacrylic acid ester, acrylic acid is used as di-,
There are methods of reacting with tri- and tetrahydroxyl compounds to form diesters, triesters or tetraesters. For example, acrylic acid can be reacted with ethylene glycol to produce ethylene glycol diacrylate. The above polyfunctional acrylic ester monomer and polyfunctional methacrylic ester monomer are
Can be used alone or in combination of two or more,
It is preferable to use two different monomers in combination.

The oligomers from the polyfunctional (meth) acrylic acid ester monomers used for the photocurable resin are (meth) acrylate-modified polymers obtained by (meth) acrylateizing the oligomers from these monomers. This (meth) acrylate-modified polymer contains an ultraviolet-reactive (meth) acrylate group in the polymer and is usually represented by the general formula (I1I)

[0021]

[Chemical 7]

[In the formula, e is an integer of 1 to 5, and Polymer
r is an e-valent polymer, and (Meth) Acrylate is a (meth) acrylic acid ester. ] Is represented. Here, the bifunctional polymer in which e is 2 has the following structure. (Meth) Acrylate-Polymer- (Meth) Acrylate The trifunctional polymer in which e is 3 has the following structure.

[0023]

[Chemical 8]

Accordingly, the polymer having a monofunctional (meth) acrylate bound thereto has the general formula (IV)

[0025]

[Chemical 9]

(Wherein R is hydrogen or a methyl group,
Polymer and e are the same as above. ).
Further, the polymer to which the polyfunctional (meth) acrylate is bound has the general formula (V)

[0027]

[Chemical 10]

(In the formula, R, Polymer and e are the same as above. In addition, R ³ is a divalent hydrocarbon group, and h is 1 to 6.) And, a polymer in which both monofunctional and polyfunctional (meth) acrylate groups are bonded is represented by the general formula (VI)

[0029]

[Chemical 11]

(In the formula, R, Polymer, h and R ³ are the same as above. Further, f and g are integers of 1 to 3, and f
And the sum of g does not exceed 5. ). Typical examples of such a (meth) acrylate-modified polymer include those represented by the general formula (VII)

[0031]

[Chemical 12]

An acrylate polyester represented by the formula (wherein i is 1 to 20), a general formula (VIII)

[0033]

[Chemical 13]

An acrylate epoxy represented by the formula (wherein i is 1 to 20), a general formula (IX)

[0035]

[Chemical 14]

Examples include acrylate urethane represented by: Other (meth) acrylate modified polymers include (meth) acrylate alkyd urethane,
Examples thereof include (meth) acrylate polycaprolactone and (meth) acrylate unsaturated acid-modified drying oil.

In providing the intermediate layer of the photocurable resin using the above-mentioned polyfunctional (meth) acrylic acid ester monomers or oligomers of these monomers,
An ultraviolet absorber and a light stabilizer are used at the same time to accelerate the photopolymerization reaction. That is, it is an active UV absorber selected from hydroxybenzophenones, benzotriazoles, cyanoacrylates or mixtures thereof. These UV absorbers are active rather than latent absorbers. These are active U exposed to UV radiation as in the case of resorcinol monobenzoate.
It absorbs UV light from the beginning rather than changing to a V absorber. Here, as the hydroxybenzophenones, for example, 2,2′-dihydroxybenzophenone; 2,
2 ', 4,4'-tetrahydroxybenzophenone;
2,2'-dihydroxy-4,4'-dimethoxybenzophenone;2,2'-dihydroxy-4,4'-diethoxybenzophenone;2,2'-dihydroxy-4,
4'-dipropoxybenzophenone;2,2'-dihydroxy-4-methoxy-4'-ethoxybenzophenone;2,2'-dihydroxy-4-methoxy-4'-propoxybenzophenone;2,3'-dihydroxy-
4,4'-dimethoxybenzophenone;2,3'-dihydroxy-4-methoxy-4'-butoxybenzophenone; 2, -dihydroxy-4,4 ', 5'-trimethoxybenzophenone;2-hydroxy-4,4' , 6'-
Tributoxybenzophenone; 2-hydroxy-4-butoxy-4 ', 5'-dimethoxybenzophenone; 2-
Hydroxy-4-ethoxy-2 ', 4'-dibutylbenzophenone;2-hydroxy-4-propoxy-4',
5'-dichlorobenzophenone; 2-hydroxy-4-
Propoxy-4 ', 5'-dibromobenzophenone;
2,4-dihydroxybenzophenone; 2-hydroxy-4-methoxybenzophenone; 2-hydroxy-4-
Ethoxybenzophenone; 2-hydroxy-4-methoxy-4'-methylbenzophenone; 2-hydroxy-4
-Methoxy-4'-ethylbenzophenone;2-hydroxy-4-methoxy-4'-chlorobenzophenone; 2
-Hydroxy-4,4'-dimethoxybenzophenone;
2-Hydroxy-4,4'-dimethoxy-3-methylbenzophenone;2-Hydroxy-4,4'-dimethoxy-2'-ethylbenzophenone; 2-Hydroxy-4-
Ethoxy-4'-methylbenzophenone;2-hydroxy-4-ethoxy-4'-methoxybenzophenone; 2
-Hydroxy-4,4'-diethoxybenzophenone;
2-Hydroxy-4-ethoxy-4'-propoxybenzophenone;2-Hydroxy-4-ethoxy-4'-chlorobenzophenone; 2-Hydroxy-4-ethoxy-
4'-bromobenzophenone and the like can be mentioned.

Examples of benzotriazoles include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole: 2- (2'-hydroxy-).
5'-t-butylphenyl) benzotriazole: 2-
(2'-Hydroxy-3'-methyl-5'-t-butylphenyl) benzotriazole: 2- (2'-hydroxy-5'-cyclohexylphenyl) benzotriazole: 2- (2'-hydroxy-3 ', 5'-Dimethylphenyl) benzotriazole: 2- (2'-hydroxy-5'-t-butylphenyl) -5-chlorobenzotriazole: 2- (2'-hydroxy-3'-di-t-butylphenyl) Examples thereof include benzotriazole.

Among the cyanoacrylates useful as the ultraviolet absorber, the compound represented by the general formula (X)

[0040]

[Chemical 15]

(In the formula, R ⁴ represents alkyl, cyclosylalkyl, hydroxyalkyl or hydroxycycloalkyl, and R ⁵ is independently a monovalent hydrocarbon group, a halogen atom, a hydroxy group or a monovalent hydrocarbon oxy group. Selected from the groups, and e is independently 0
Is an integer of ~ 5. ). Typical examples thereof include ethyl-2-cyano-3,3-diphenyl acrylate.

On the other hand, as the light stabilizer used for imparting weather resistance, those having a cyclic hindered amine structure are preferable. The light stabilizer having a cyclic hindered amine structure has the general formula (XI)

[0043]

[Chemical 16]

(In the formula, k represents an integer of 1 to 4, and R
⁶ is an acyl group derived from an aliphatic or aromatic monocarboxylic acid when k = 1, a diacyl group or a carbonyl group derived from an aliphatic or aromatic dicarboxylic acid when k = 2, k = 3, a triacyl group derived from an aliphatic or aromatic tricarboxylic acid is
When k = 4, it represents a tetraacyl group derived from an aliphatic or aromatic tetracarboxylic acid. ). Specifically, for example, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine; 4-hexanoyloxy-2,2,6,6-tetramethylpiperidine; 4-octanoyloxy-2,2 , 6,6-Tetramethylpiperidine; 4-stearoyloxy-2,
2,6,6-Tetramethylpiperidine; succinic acid-bis (2,2,6,6-tetramethyl-4-piperidyl);
Sebacic acid-bis (2,2,6,6-tetramethyl-4
-Piperidyl); phthalic acid-bis (2,2,6,6-tetramethyl-4-piperidyl); trimesic acid-tris (2,2,6,6-tetramethyl-4-piperidyl) and the like. These light stabilizers having a cyclic hindered amine structure can improve excellent weather resistance even in a small amount, and are very useful for stabilization. The blending amount with respect to the monomer or oligomer is 0.01 to 20 parts by weight. If the amount is less than 0.01 part by weight, the effect is not remarkable, and if it exceeds 20 parts by weight, the intermediate layer may be whitened or haze may occur, which is not preferable. These light stabilizers may be used alone or in combination of two or more.

When these light stabilizers having a cyclic hindered amine structure are used, it is preferable to further use an antioxidant. The reason for this is not clear, but when these light stabilizers are used in combination with an antioxidant, the effects of improving the weather resistance and stabilizing effect of the light stabilizer having a cyclic hindered amine structure are further synergistically exhibited. As for the amount of the antioxidant used, a small amount is sufficient, and it is 0.01 to 2.0 parts by weight based on the monomer or oligomer. When the amount is less than 0.01 parts by weight, the synergistic effect with the light stabilizer is small, and when the amount is more than 2.0 parts by weight, the intermediate layer may be whitened or haze may occur, resulting in deterioration of appearance. There is. Examples of the antioxidant include octadecyl-
3- (3,5-ditertiarybutyl-4-hydroxyphenyl) -propionate; pentaerythrityl-tetrakis [5- (3,5-ditertiarybutyl-4-hydroxyphenyl) -propionate]; 1,6-hexane Diol bis-3- (3,5-ditertiary butyl-
4-hydroxyphenyl) -propionate; 2,2 '
-Thiodiethylbis- [5- (3,5-ditertiarybutyl-4-hydroxyphenyl) -propionate];
2,4-bis (n-octylthio) -4- (4-hydroxy-3,5-ditertiarybutylanilino) -1,
3,5-triazine; 3,5-ditertiarybutyl-4
-Hydroxybenzene phosphoric acid diethyl ester; 1,
3,5,6-Tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid;
4-methyl-2,6-ditertiarybutylphenol;
4-methyl-2,6-bis (1-methylheptadecyl)
-Phenol; 2,2'-methylenebis (4-ethyl-
6-tert-butylphenol); 1,3,5-tris (4-hydroxy-1,3-ditertiarybutylbenzyl) -2,4,6-trimethylbenzene and the like. These may be used alone or in combination of two or more.

The thermoplastic resin used for providing the intermediate layer on the substrate has a tensile modulus of 2,000 MP.
It has a characteristic smaller than that of a, and specific examples thereof include acrylic resin, polyurethane resin, polycarbonate resin, polyester resin, and fluororesin. To provide an intermediate layer on the substrate using the thermoplastic resin or the thermosetting resin, first, the thermoplastic resin or the thermosetting resin is dissolved or dispersed in water or an organic solvent to form a resin solution. Prepare. Then, an intermediate layer can be provided by coating and drying the resin solution on the substrate by a commonly used coating method. Here, in preparing the resin solution, examples of the organic solvent provided include ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, aromatic hydrocarbons such as benzene, toluene and xylene, halogens such as chloroform and methylene chloride. Hydrocarbons, methanol, ethanol, propanol,
Alcohols such as butanol, tetrahydrofuran,
Examples include organic solvents such as ethers such as dioxane, and cellosolves such as ethyl cellosolve and butyl cellosolve. These may be used alone or 2
Mixtures of more than one species may be used. Then, in order to provide an intermediate layer of a photocurable resin on the substrate, first, the polyfunctional (meth) acrylic acid ester monomer or an oligomer thereof, an ultraviolet absorber or a light stabilizer and, if necessary, an oxidant are used. A photocurable composition solution is prepared by dissolving an inhibitor and other auxiliaries in an organic solvent. Then, the photocurable composition solution is applied onto the substrate by a coating method which is usually carried out in the same manner as described above, and then an intermediate layer of the photocurable resin can be provided by irradiating with ultraviolet rays. As the organic solvent used for preparing the photocurable composition solution, the above organic solvent can be used in the same manner. The thickness of the intermediate layer thus provided on the substrate is 1 to 50 μm, preferably 3 to 10 μm,
The objectives aimed at in the present invention can be achieved.

The phosphazene resin-coated member of the present invention is
Thus, it can be obtained by providing the intermediate layer on the substrate and providing the surface layer of the phosphazene-based cured resin on the intermediate layer. Here, the phosphazene-based curable resin forming the surface layer has a curable phosphazene compound as an essential component, and optionally a curable phosphazene compound as a main component and a monomer copolymerizable with the other, and other additives. It is a polymer obtained by blending and polymerizing. Examples of the curable phosphazene compound include compounds represented by the general formula (X
II)

[0048]

[Chemical 17]

[In the formula, A represents a polymerization-curable group, and B represents a non-polymerization-curable group. Further, a and b are 0 <a and 0 ≦ b
And a real number that satisfies a + b = 2. ] The phosphazene compound etc. which have a repeating unit represented by these are mentioned, and there exist various things according to the kind of each substituent. In the formula, A
Represents a polymerization-curable group, and the polymerization-curable group means a functional group that is cured by reaction with irradiation of ultraviolet rays, visible rays or electron beams, use of a chemical curing agent or heating, and is usually It is a group having a reactive double bond. There are various groups having this reactive double bond. For example,
Functional groups containing an acryloyl group, a methacryloyl group, a vinyl group, or an allyl group are mentioned. The functional group containing an acryloyl group or a functional group containing a methacryloyl group is an acryloyloxy group or a methacryloyloxy group,
Furthermore, the general formula (XIII)

[0050]

[Chemical 18]

[In the formula, R ⁷ represents a hydrogen atom or a methyl group, and R ⁸ represents an alkylene group having 1 to 12 (preferably 1 to 5) carbon atoms (including a branched alkylene group). ] Is represented.

Specific examples of the group represented by the general formula (XIII) include 2-hydroxyethyl methacrylate and 2-hydroxyethyl methacrylate.
Hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 6-hydroxy-3-methylhexyl methacrylate, 5-hydroxyhexyl methacrylate, Hydroxyl groups in methacrylates such as 3-hydroxy-2-t-butylpropyl methacrylate, 3-hydroxy-2,2-dimethylhexyl methacrylate, 3-hydroxy-2-methyl-2-ethylpropyl methacrylate and 12-hydroxydodecyl methacrylate From the residue except hydrogen atom, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxy Propyl acrylate, 2-hydroxybutyl acrylate, 3-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, 6-hydroxy-3-methylhexyl acrylate, 5-hydroxyhexyl acrylate, 3-hydroxy-2-t -Butylpropyl acrylate, 3-hydroxy-2,2-dimethylhexyl acrylate, 3-hydroxy-2-methyl-2-
Examples thereof include a residue obtained by removing a hydrogen atom from a hydroxyl group in acrylates such as ethylpropyl acrylate and 12-hydroxydodecyl acrylate. Particularly preferred groups are 2-hydroxyethyl methacrylate residue and 2-hydroxyethyl acrylate residue.
Further, the functional group containing an acryloyl group or a methacryloyl group, in addition to the above general formula (XIII), a general formula (X
IV)

[0053]

[Chemical 19]

[In the formula, R ⁷ and R ⁸ are the same as defined above. ] A functional group represented by, that is, a residue obtained by removing a hydrogen atom from a hydroxyl group of hydroxyalkyl-substituted (meth) acrylamide, further represented by the general formula (XV)

[0055]

[Chemical 20]

[In the formula, R ⁷ is the same as defined above. ] A functional group represented by the following, that is, a residue obtained by removing one hydrogen atom from an amino group of acrylamide or methacrylamide can be mentioned. Furthermore, as the functional group containing an allyl group,
In addition to the allyl group itself, for example, an allyloxy group (C
_{H 2 = CH-CH 2 O-} ) it is not limited to this allyloxy group, broadly, the general formula (XVI) ~ (XVIII)

[0057]

[Chemical 21]

[In the formula, R ⁷ , R ⁹ and R ¹⁰ are the same as described above. ] A functional group represented by the following, that is, a residue obtained by removing a hydrogen atom from the hydroxyl group of an allyl compound having one hydroxyl group can be mentioned. Specific examples of the functional groups represented by the general formulas (XVI) to (XVIII) include those represented by the formula:

[0059]

[Chemical formula 22]

There is a residue obtained by removing a hydrogen atom from a hydroxyl group in an allyl compound represented by, for example. On the other hand, the general formula (XII)
B in the general formula (XIX), (XX) is as described above.

[0061]

[Chemical formula 23]

[In the formula, M is an oxygen atom, a sulfur atom or
Represents a mino group, R¹¹Is an alkyl group having 1 to 18 carbon atoms
Or represents a halogenated alkyl group having 1 to 18 carbon atoms. Well
R ¹²~ R¹⁶Are independently hydrogen atom and halogen atom
Child, alkyl group having 1 to 4 carbon atoms or ha having 1 to 4 carbon atoms
A rogenated alkyl group is shown. ] The group represented by is shown. one
Specific examples of general formula (XIX) include methoxy group and ethoxy group.
Group, propoxy group, butoxy group, pentyloxy group,
Xyloxy group, heptyloxy group, octyloxy group
Alkoxy groups such as, halogen (eg fluorine, chlorine,
A similar alkoxy group substituted with bromine, etc., methyl
O group, ethylthio group, propylthio group, butylthio group,
Pentylthio group, heptylthio group, octylthio group, etc.
Alkylthio group, halogen (eg fluorine, chlorine, odor
A similar alkylthio group substituted with
Mino group, ethylimino group, propylimino group, butyrui
Mino group, pentylimino group, hexyluimino group, hepti
Alkylimino such as ruimino group and octylimino group
Substitute with groups or halogens (eg fluorine, chlorine, bromine, etc.)
The similar alkylimino group etc.
It The group of formula (XX) is specifically a phenoxy group or thiof
Phenyl group, halogenated phenoxy group (2,4,6-tri
Bromophenoxy group, 4-bromophenoxy group, 2-
Rolophenoxy group, 2,4-dichlorophenoxy group
And halogenated thiophenyl group (4-chlorophene)
Nylthio group) or aniline and halogenated
Aniline (2-chloroaniline, 2,4-dichloroaniline
Amino of phosphorus, 2,4,6-tribromoaniline, etc.
Examples include residues in which hydrogen atoms have been removed from groups.
Wear.

Regarding a and b in the above general formula (XII), 0 <a ≦ 2, 0 ≦ b <2, and a + b =
It may be any real number satisfying 2, but preferably 0.6 ≦ a ≦
2,0 ≦ b ≦ 1.4. The substituent A has the general formula (XI
When the phosphazene compound of I) is polymerized (cured), it is a group that exerts a curing action, and the substituent B is a group that exerts the action of regulating the physical properties of the polymer and the polymerization performance. However, since those with a = 0 do not have curability, such phosphazene compounds are excluded from the scope of the present invention. However, a = 2, b = 0, that is,

[0064]

[Chemical formula 24]

[In the formula, A is the same as above. ] The phosphazene compound having a repeating unit represented by the following can be used as a raw material in the present invention, and can make the present invention more effective in terms of curability. Preferred curable phosphazene compounds used in the present invention include:
It has a repeating unit of the above-mentioned general formula (XII), but its degree of polymerization is 3 or more, preferably in the range of 3 to 10,000, more preferably in the range of 3 to 18, especially 3 or 4 or A mixture thereof is optimal.
In addition, the repeating units of general formula (XII) are linked (polymerized) in a chain form.
Some of them are formed, but those formed by ring-shaped bonding (polymerization) are preferable. Specific examples of such a curable phosphazene compound are as follows.

[0066]

[Chemical 25]

Such a curable phosphazene compound is
It can be manufactured by various methods and is not particularly limited. For example, when it is desired to introduce a group represented by the general formula (XIII) as the substituent A, a hydroxyalkyl (meth) acrylate corresponding to the general formula (XIII), that is, a general formula

[0068]

[Chemical formula 26]

[In the formula, R ⁷ and R ⁸ are the same as defined above. ]
When using a hydroxyalkyl (meth) acrylate represented by and introducing a group represented by the general formula (XIV) as the substituent A, the corresponding general formula

[0070]

[Chemical 27]

[In the formula, R ⁷ and R ⁸ are the same as defined above. ]
When using a hydroxyalkyl (meth) acrylamide represented by the formula (1) and introducing a group represented by the general formula (XV) as the substituent A, the corresponding general formula

[0072]

[Chemical 28]

[In the formula, R ⁷ is the same as above. ] When using the (meth) acrylamide represented by the following or when it is desired to introduce the group represented by the general formula (XVI) to (XIX) as the substituent A, the corresponding general formula

[0074]

[Chemical 29]

[In the formula, R ⁷ , R ⁹ and R ¹⁰ are the same as defined above. ] Allyl alcohol, allyl phenol, allyl ester of hydroxybenzoic acid or its derivative represented by On the other hand, the general formula introduced as the substituent B
In the group represented by (XIX), when M is an oxygen atom, R ¹¹ OH [wherein R ¹¹ is the same as defined above. ] Alkanol represented by
Using halogenated alkanol or its derivative, M
Is a sulfur atom, R ¹¹ SH [wherein R ¹¹ is the same as above. ] An alkyl mercaptan represented by the following formula, a halogenated alkyl mercaptan or a derivative thereof is used, and when M is an imide group, R ¹¹ NH ₂ [wherein R ¹¹ is the same as above]. ] An alkylamine, a halogenated alkylamine or a derivative thereof represented by In the group represented by the general formula (XX) to be introduced as the substituent B, when M is an oxygen atom, the general formula

[0076]

[Chemical 30]

[In the formula, R ^{12 to} R ¹⁶ are the same as described above. ] When phenols represented by the following are used and M is a sulfur atom,

[0078]

[Chemical 31]

[In the formula, R ^{12 to} R ¹⁶ are the same as described above. ] When thiophenols represented by

[0080]

[Chemical 32]

[In the formula, R ^{12 to} R ¹⁶ are the same as defined above. ] An aniline or its derivative represented by The compound forming the substituent A and the compound forming the substituent B are mixed with chlorophosphazene (a cyclic compound represented by the formula (NPCl ₂ ) _n or a compound represented by the formula Cl ₄ P. (NPCl ₂ ) _n- 1.N.
The desired curable phosphazene compound of the general formula (XII) can be obtained by reacting with a chain compound represented by PCl ₃ (n is an integer of 3 or more, preferably 3 to 18). When the compound forming the substituent B is an alcohol, a mercaptan, a phenol or a thiophenol, an alcoholate, a phenolate or a mercaptide is previously reacted with an alkali metal such as sodium metal or potassium metal. , It may be stored as thiophenolates. Further, in the reaction of the compound forming each of the substituents A and B with chlorophosphazene, it is preferable to use a dehydrohalogenating agent such as a tertiary amine. Examples of the tertiary amine include trimethylamine, triethylamine, triisopropylamine, tri-n-propylamine, tri-n-butylamine, pyridine, and the like. Of these, pyridine is preferable. Furthermore, this reaction is usually performed in an organic solvent. Examples of the organic solvent include benzene,
Toluene, xylene, chloroform, cyclohexane,
Mention may be made of methylene chloride, tetrahydrofuran, 1,4-dioxane and the like. These can be used alone or in combination. In the curable phosphazene compound obtained by the above reaction, it is preferable that all the chlorine atoms of chlorophosphazene which is a raw material be substituted with the above-mentioned substituents, but some chlorine may remain.

In the present invention, the phosphazene-based curable resin for the surface layer contains the above-mentioned curable phosphazene compound as an essential component, and optionally a monomer (for copolymerization) copolymerizable with the above-mentioned curable phosphazene compound. It can be obtained by applying and polymerizing a curable composition containing a UV absorber, an antistatic agent, an antifogging agent, a lubricant and the like as a monomer) or other additives. The monomer copolymerizable with the curable phosphazene compound (copolymerization monomer) has a silicone-modified curable compound, a polymerizable prepolymer, and further an acryloyl group, a methacryloyl group, a vinyl group or an allyl group. Examples thereof include compounds having a reactive double bond, such as polymerizable monomers. Here, the silicone-modified curable compound is not particularly limited as long as it is a compound having a silicone (silane) group and preferably a (meth) acrylate group in one molecule.

Specific examples of the silicone-modified curable compound include silicone-modified urethane acrylate, (meth) acryloxysilane compound, and (meth) acrylate-modified polysiloxane. Examples of the (meth) acryloxysilane compound include γ-methacryloxypropyltrimethoxysilane and γ-methacryloxypropylmethyldimethoxysilane. As the (meth) acrylate-modified polysiloxane, there is a compound containing a silicone (silane) group and a (meth) acrylate group in one molecule. The mixing ratio of the curable phosphazene compound and the silicone-modified curable compound is not particularly limited and may be appropriately selected depending on the type of the silicone-modified curable compound.
Usually, the curable phosphazene compound is 20 to 99.5 parts by weight, and the silicone-modified curable compound is 0.5 to 80 parts by weight. Curable phosphazene compounds 40 to 99 are preferred.
Parts by weight, 1 to 60 parts by weight of the silicone-modified curable compound.

Specific examples of the polymerizable monomer having an acryloyl group, a methacryloyl group, etc. include methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and 2-hydroxyethyl (meth).
Monofunctional groups such as acrylate and 2-hydroxypropyl (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth)
Acrylate, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, neopentyl glycol Bifunctional groups such as di (meth) acrylate, polyethylene glycol di (meth) acrylate, hydroxybivalate neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, Examples thereof include polyfunctional compounds having three or more functional groups such as dipentaerythritol hexa (meth) acrylate.

On the other hand, specific examples of the polymerizable prepolymer include polyester (meth) acrylate, polyurethane (meth) acrylate, epoxy (meth) acrylate, polyether (meth) acrylate, melamine (meth) acrylate and oligo. Prepolymers having at least one (meth) acryloyl group such as (meth) acrylate, alkyd (meth) acrylate, polyol (meth) acrylate, and silicon (meth) acrylate may be mentioned. Particularly preferred prepolymers are polyester, epoxy and polyurethane (meth) acrylates. Examples of the polyester (meth) acrylate include ethylene glycol, 1,4-butadiol, 1,6-hexanediol, diethylene glycol trimethylolpropane, dipropylene glycol, polyethylene glycol, polypropylene glycol, pentaerythritol, and dipentaerythritol. A polyester is obtained from a polyhydric alcohol and a polybasic acid such as phthalic acid, adipic acid, maleic acid, trimellitic acid, itaconic acid, succinic acid, terephthalic acid, and alkenylsuccinic acid, which is then (meth) acrylated. The ones that have been done are listed. As the above (meth) acrylated one, adipic acid / 1,6-hexanediol /
Examples thereof include (meth) acrylic acid-based, phthalic anhydride / propylene oxide / (meth) acrylic acid-based, trimellitic acid / diethylene glycol / acrylic acid-based polyester (meth) acrylates. Epoxy (meth) acrylate is obtained by esterifying an epoxy group of an epoxy resin with (meth) acrylic acid to make a functional group a (meth) acryloyl group. Specific examples of this include bisphenol A-epichlorohydrin type epoxy resin /
(Meth) acrylic acid type, phenol novolac-epichlorohydrin type epoxy resin / (meth) acrylic acid type,
Examples thereof include alicyclic epoxy resin / (meth) acrylic acid-based epoxy (meth) acrylate. As the polyurethane (meth) acrylate, for example, by reacting an isocyanate compound such as tolylene diisocyanate with a (meth) acrylate having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, can get. In this case, the central part of the molecule often has a polyester structure, and is often (meth) acrylated by disposing isocyanate groups at both ends. Examples of urethane compounds include oil-modified polyurethane resin systems, moisture-curable polyurethane resin systems, block-type polyurethane resin systems and catalyst-curable polyurethane resin systems. Specific examples of the epoxy compound include those obtained by adding a suitable curing agent to an epoxy resin, those esterified by the reaction of an epoxy resin with a fatty acid, and those using a combination of an epoxy resin and an alkyd resin. .

Using the curable phosphazene compound or the monomer copolymerizable with the curable phosphazene compound,
In order to provide a surface layer on a substrate via an intermediate layer, a curable composition containing the curable phosphazene compound as an essential component is prepared, and the curable composition is applied and cured. . A normal temperature curing method can be used to apply and cure the curable composition containing the curable phosphazene compound as an essential component, but in consideration of the characteristics of the resulting cured resin surface layer, a heat curing method and Active energy ray (visible light, ultraviolet ray, electron beam, X
It is preferable to use a method of curing by irradiating with rays or γ rays). Therefore, when preparing a curable composition containing the curable phosphazene compound as an essential component, the preparation method is changed depending on the curing method after polymerization or copolymerization of the curable phosphazene compound.
That is, when a heat curing method is used when carrying out the above-mentioned polymerization or copolymerization, it is preferable to use a peroxide compound or an azo compound as a polymerization initiator, singly or in combination, if necessary. Here, as the peroxide-based compound, specifically, for example, benzoyl peroxide; p-chlorobenzoyl peroxide; 2,
4-dichlorobenzoyl peroxide; t-butyl hydroperoxide; di-t-butyl peroxide;
Examples thereof include dicumyl peroxide; t-butyl peroxyacetate; t-butyl peroxybenzoate. Other peroxides (persulfate, redox type) can also be used. Examples of the persulfate include ammonium persulfate and potassium persulfate, and as the redox type, hydrogen peroxide-metal salt. , Organic peroxide-metal salt, organic peroxide-aliphatic or alicyclic polyamine compound, organic peroxide-dimethylaniline,
Examples of azo compounds such as potassium dichromate-metal oxides include aromatic diazoamino compounds, aromatic diazothioethers, aromatic diazooxy compounds, and aliphatic diazo compounds. In the heat curing method, it may be completely cured at 100 ° C. or higher, though it depends on the conditions such as the coating amount and the coating speed of the curable composition.

On the other hand, when carrying out the above-mentioned polymerization or copolymerization,
When utilizing a curing method using active energy rays such as ultraviolet rays, electron rays or visible rays, it is preferable to use a polymerization initiator (photosensitizer), if necessary. As the polymerization initiator, various kinds can be used. Specifically, for example, 1-hydroxycyclohexyl phenyl ketone, dibenzoyl, benzoyl, benzoin methyl ether, benzoin ethyl ether, p-chlorobenzophenone, p-methoxybenzophenone, benzoyl peroxide, di-t-butyl peroxide, camphorquinone and the like. Can be mentioned. These reaction initiators can be used alone or in combination. The amount of these polymerization initiators to be added is usually 0.05 to 100 parts by weight of the curable phosphazene compound.
Used in the range of 1.0 parts by weight. In this curing method using active energy rays, for example, in the case of ultraviolet rays, the ultraviolet rays having a wavelength in the range of 200 to 550 nm are set to 0.
Irradiation may be performed for 1 second or longer, preferably 0.5 to 30 seconds. Here, the integrated light quantity of the irradiation light is usually 100 to 5.0.
It is 00 mJ / cm ² . The amount of the polymerization initiator used is usually selected in the range of 0.1 to 5.0 parts by weight with respect to 100 parts by weight of the curable compound.

An example of the component composition of the curable composition prepared by providing the surface layer of the phosphazene-based curable resin is as follows. (A) 100 parts by weight of curable phosphazene compound (b) 0 to 100 parts by weight of monofunctional monomer and / or polyfunctional monomer copolymerizable with curable phosphazene compound (c) solvent (d) light Reaction initiator or thermal polymerization initiator 0.05 to 10 parts by weight [relative to 100 parts by weight of (a) and (b)] (e) Other additives

In the present invention, the curable composition thus prepared is applied onto a substrate via an intermediate layer,
To cure, but to apply the curable composition, a coater generally used for ordinary coating (eg, gravure coater, roll coater, curtain coater, bar coater, blade coater, doctor coater, spray coater, etc. ), And then the solvent is removed if necessary. Then, the surface layer of the phosphazene-based cured resin can be formed by curing with the above-described curing method. The thickness of the surface layer thus formed is usually 0.03 to 2.0 μm, preferably 0.1 to 1.0.
With a thickness of μm, a phosphazene-based resin coating member (see FIG. 1) having excellent quality can be obtained.

[0090]

EXAMPLES Next, the present invention will be described in more detail with reference to Examples and Comparative Examples. Production Example 1 [Production of Curable Phosphazene Compound (A)] 55.0 g of hexachlorocyclotriphosphazene (hereinafter abbreviated as 3PNC) was placed in a 1-liter flask equipped with a thermometer, a stirrer, a dropping funnel and a condenser. 0.167
Mol), toluene 50 ml and pyridine 15
8 g (2.0 mol) was added and stirring was started. Then 2
-143 g (1.1 mol) of hydroxyethyl methacrylate (hereinafter abbreviated as HEMA) was gradually added dropwise from the dropping funnel. The mixture was heated to 80 ° C. in a warm bath and the reaction was carried out for 8 hours with stirring. Next, the precipitated crystals and the solvent in the filtrate were removed by vacuum distillation, and the filtrate was thoroughly dried to give a yellow liquid 1,1,3,3,5,5-hexa (methacryloylethylenedioxy) cyclotriphosphazene. 136 g of [curable phosphazene compound (A)] was obtained. The yield was 91%.

Production Example 2 [Production of Curable Phosphazene Compound (B)] 2 equipped with a thermometer, a stirrer, a dropping funnel and a condenser
After adding 300 ml of tetrahydrofuran and 25.5 g of metallic sodium to a liter flask, 104.3 g (1.11 mol) of phenol was added dropwise to the flask, and after completion of the dropping, the mixture was refluxed for 3 hours to obtain a phenolate. . Next, hexachlorocyclotriphosphazene 193
A solution prepared by dissolving g (0.555 mol) in 400 ml of benzene was dropped into a tetrahydrofuran solution containing the above phenolate, and the reaction was allowed to proceed under reflux for 4 hours. Then, the temperature of the reaction solution was cooled to room temperature, 352 g (4.45 mol) of pyridine was added, and further,
2-hydroxyethyl methacrylate 381 g (2.45
Mole) was gradually added dropwise from the dropping funnel and then at 20 ° C at 20 ° C.
It was made to react over time. Then, the precipitated crystals and catalyst were filtered off, the solvent in the obtained filtrate was removed by distillation under reduced pressure, and the residue was thoroughly dried to obtain 452 g of a yellow liquid [curable phosphazene compound (B)].

Example 1 Composition of intermediate layer By weight Bifunctional urethane acrylate 80 [Somar Co., trade name, SARTOMER 9640] Bifunctional polyether acrylate 12 [Nippon Kayaku Co., trade name, KAYARAD PEG400DA ] Mixture of dipentaerythritol monohydroxypentaacrylate and dipentaerythritol hexaacrylate 8 [Nippon Kayaku Co., Ltd., trade name, KAYARAD DPHA] 1-hydroxycyclohexyl phenyl ketone (photoinitiator) 3 [Ciba Geigy, trade Name, Irgacure 184] Methyl-3- [3- (2Hbenzotriazol-2-yl) -5-tetrabutyl-4-hydroxyphenylpropionel and polyethylene glycol mixture (UV absorber) 10 [Ciba Geigy, trade name , Tinuvin 1130] Toluene 50 Isoprovir alcohol 50 Methyl cellosolve 100 A coating composition having the above composition was prepared and applied on a substrate of a transparent polycarbonate sheet having a thickness of 3 mm and degreased with isopropyl alcohol with a bar coater and left at room temperature for 1 minute. It was dried at 0 ° C for 10 minutes. Then, an ultraviolet curing machine [VMC type manufactured by Ushio Inc.] was irradiated with ultraviolet rays of 500 mJ / cm ² to form an intermediate layer having a thickness of 10 μm. This intermediate layer is 40 ℃ measured separately on the test piece
The coefficient of thermal expansion was 6.0 × 10 ⁻⁵ cm · cm ⁻¹ · ° C. ⁻¹ .

Cured resin surface layer Compounding composition Weight part Curable phosphazene compound (A) 40 6-functional urethane acrylate 30 [manufactured by Kyoeisha Oil & Fat Co., Ltd., trade name, UA-306H] Bifunctional urethane acrylate 30 [manufactured by Somar Co., Ltd.] , Trade name, SARTOMER 9505] Colloidal silica (alcohol dispersion liquid) 100 [Catalyst Kasei Co., Ltd., trade name, Oscar 1432] 2-hydroxycyclohexyl phenyl ketone (photoinitiator) 3 [Ciba Geigy, trade name, dolphin Cure 184] HALS (light stabilizer) 1 [manufactured by Ciba-Geigy, trade name, Tinuvin 144] Butanol 50 Methyl isobutyl ketone 80 A paint was prepared with the above composition, and applied on the intermediate layer with a bar coater at room temperature. After left for 1 minute, it was dried at 80 ° C. for 10 minutes. Then, an ultraviolet ray of 500 mJ / cm ² was irradiated to form a surface layer having a thickness of 8 μm to obtain a phosphazene resin-coated member.

Example 2 A phosphazene resin coating was carried out in the same manner as in Example 1 except that the curable phosphazene compound (A) was replaced with the curable phosphazene compound (B) of Production Example 2. The member was obtained. Example 3 A phosphazene resin-coated member was obtained in the same manner as in Example 1 except that a polymethylmethacrylate sheet having a thickness of 3 μm was used as the substrate in place of the polycarbonate sheet.

Example 4 Intermediate layer Blend composition Weight part Hydroxyethyl methacrylate: methyl acrylate: copolymer of methyl methacrylate = 10: 10: 80 (degree of polymerization 500) 20 hexamethylene diisocyanate (curing agent) 4 UV absorber (implementation (Same as Example 1) 2 Toluene 20 Ethyl acetate 34 Isopropyl alcohol 20 A coating composition having the above composition was prepared and applied on a substrate of a transparent polycarbonate sheet having a thickness of 3 mm degreased with isopropyl alcohol with a bar coater at room temperature. After leaving it for 1 minute, it was dried at 80 ° C. for 30 minutes. As a result, an intermediate layer of curable resin having a thickness of 8 μm was formed. This intermediate layer has a coefficient of thermal expansion at 40 ° C, which was separately measured with a test piece.
It was 6.5 × 10 ⁻⁵ cm · cm ⁻¹ · ° C. ⁻¹ . Then, in the same manner as in Example 1, a surface layer having a thickness of 8 μm was formed on this intermediate layer to obtain a phosphazene resin-coated member.

Example 5 Composition of intermediate layer Part by weight Copolymer of methyl methyl methacrylate and methyl methyl acrylate 18 [90:10 (weight ratio), number average molecular weight 1,200] UV absorber (Example 1 The same) 2 Methyl ethyl ketone 28 Butanol 28 Diacetone alcohol 24 A paint having the above composition is prepared and applied on a substrate of a transparent polycarbonate sheet having a thickness of 3 mm degreased with isopropyl alcohol with a bar coater, and at room temperature for 1 minute. After standing, it was dried at 80 ° C. for 10 minutes. As a result, an intermediate layer of thermoplastic resin having a thickness of 5 μm was formed. The tensile elastic modulus of the thermoplastic resin of this intermediate layer was 1,000 MPa. Then, in the same manner as in Example 1, a surface layer having a thickness of 8 μm was formed on this intermediate layer to obtain a phosphazene resin-coated member.

Comparative Example 1 Example 1 was repeated except that the intermediate layer was not formed.
A phosphazene resin-coated member for comparison was obtained in the same manner as in Example 1. Comparative Example 2 Commercially available acrylic coating material [manufactured by Fujikura Kasei Co., Ltd.,
A phosphazene resin-coated member for comparison was obtained in the same manner as in Example 1 except that the cured resin surface layer was formed by using Fujihard EXP1951HK-N7, trade name.

Various tests were carried out as performance evaluations on the phosphazene resin-coated members obtained in Examples and Comparative Examples. The results of performance evaluation are shown in Table 1.

[0099]

[Table 1]

[0100]

[Table 2]

The performance evaluation was performed by the following method. 1) Weather resistance Sunshine Weather Ometer [Suga Test Instruments Co., Ltd.
WELSUN-HC type] It was irradiated for 1,000 hours and 2,000 hours, the appearance and yellowing of the test piece before and after irradiation were observed, and the adhesiveness was subjected to a googgle peeling test. A) Appearance evaluation criteria ⊚: No cracks or peeling of the coating film. ◯: Some cracks were observed. Δ: Cracks occurred. X: The coating film spontaneously peels off. B) Evaluation criteria for yellowing ◎: None ○: Minute △: Little ×: Remarkable c) Goggle peeling test 1 at 1 mm intervals with a cutter knife on the test piece before and after irradiation.
100 pieces of goggles were cut in a range of 0 mm × 10 mm, cellophane tape was pressure-bonded, and then peeled to observe the peeled state of the goggles to evaluate the adhesiveness. ◯: No peeling occurs. Δ: Less than 50% of the crevices are peeled off. X: 50% or more of the crevices are peeled off. 2) Abrasion resistance A Taber abrasion tester was used CS-10 (Abrasion); 500 g, 1,000 rpm The difference in haze before and after the test (Δ haze) was evaluated. Also,
Sunshine weatherometer (same as above) 1,000
The wear resistance of the test piece after the time irradiation was also evaluated in the same manner. 3) Hot water resistance The test piece was immersed in boiling water and the change in appearance was observed. In addition, sunshine weatherometer (same as above) 1,0
The hot water resistance was similarly evaluated for the test piece after irradiation for 00 hours. ◯: No change in appearance. Δ: Whitening was observed. X: Whitening and blistering occur, and peeling of the coating film is recognized.

[0102]

As described above, according to the present invention, it is possible to obtain a phosphazene resin-coated member having improved weather resistance and improved abrasion resistance due to reduction of cracks.
Therefore, the phosphazene-based resin coating member of the present invention can be effectively used widely in automobiles, building materials, vehicles, aircrafts, optical materials and the like.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of a phosphazene-based resin coating member of the present invention.

[Explanation of symbols]

 1: Substrate 2: Intermediate layer 3: Surface layer

Claims (2)

[Claims] 1. A substrate, an intermediate layer of a curable resin which is provided on the substrate and has a coefficient of thermal expansion at 40 ° C. of greater than 5 × 10 ⁻⁵ cm · cm ⁻¹ · ° C. ^−1, and the intermediate layer. A phosphazene-based resin coating member comprising a surface layer of a provided phosphazene-based cured resin. 2. A substrate, an intermediate layer of a thermoplastic resin having a tensile elastic modulus of less than 2,000 MPa provided on the substrate, and a surface layer of a phosphazene-based cured resin provided on the intermediate layer. Characteristic phosphazene resin coating member.