JP2001335646A - Sheet and film of functionalized polyphenylene ether resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the sheet and the film of a functionalized polyphenylene ether resin that have a sufficient functional properties such as a coating adhesion, are improved in surface appearance by reducing the amounts of foreign matters, and furthermore, is good in balance of the thermostability and mechanical properties, and therefore, sufficiently respond to industrial requirements. SOLUTION: Obtaining the sheet and the film, composed of (c) the functionalized polyphenylene ether resin, is characterized by reacting an admixture of (A) polyphenylene ether of 100 pts.wt. with (B) a denaturant of 0.01 to 10.0 pts.wt. selected from among a conjugated nonaromatic compound, a dienophile compound having one dienophile group or a precurser of these dienes and dienophile compounds, at a reaction temperature of room temperature or above and melting point or below of (A) polyphenylene ether.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sheet or film of a functionalized polyphenylene ether resin which can be used as a plastic material in the fields of electric / electronics, automobiles, various other industrial materials, and food / packaging.

[0002]

2. Description of the Related Art Polyphenylene ether resin has good workability.
It has excellent productivity and can efficiently produce products and parts of desired shape by molding methods such as melt injection molding and melt extrusion molding, so it can be used in the fields of electric / electronics, automobiles, various other industrial materials, foods / It is widely used as a material for products and parts in the packaging field. In recent years, in particular, products and parts have been diversified in the electric / electronic field, the automobile field, and other various industrial fields, and requirements for resin materials have been widened.

[0003] In these requirements, especially when used in the form of a sheet or a film, the outer appearance of a vehicle is required to have a good surface appearance and paint adhesion, and in the electric and electronic fields, there is a demand for adhesion to a copper plate or the like. Is growing. Ordinary polyphenylene ether resins have high heat resistance and excellent mechanical properties, but their adhesion and adhesion to metals and paints are not sufficient, and modified polyphenylene ether modified as a means for improving them Resin is commonly used.

As means for obtaining a functionalized polyphenylene ether resin by modifying polyphenylene ether, Japanese Patent Publication No. 3-52486, Japanese Patent Application Laid-Open No. 62-132924, Japanese Patent Application Laid-Open No. 63-500803, and Japanese Patent Application Laid-Open No. 5
No. 4425 discloses that polyphenylene ether is mixed with maleic anhydride or another reactable modifying compound in the presence of a radical generator or in the absence of a radical generator, and melted in a molten state such as melt kneading. Methods have been proposed for obtaining modified, functionalized polyphenylene ether resins. However, in these methods, the temperature at which the polyphenylene ether can be melt-kneaded is extremely high,
Since the melt viscosity of polyphenylene ether is very high, the reaction temperature becomes very high, and various problems have occurred.

That is, since the functionalized polyphenylene ether resin obtained by the conventional melt-kneading method has a processing temperature close to the decomposition temperature, discoloration due to thermal deterioration and sometimes foreign matters occur to cause a problem in surface appearance. In order to solve the problem of discoloration and foreign matter generation due to thermal deterioration, a method of adding a stabilizer such as a heat stabilizer and an antioxidant to polyphenylene ether and performing melt extrusion has been proposed, but the temperature of melt kneading is high. Therefore, discoloration and the number of foreign substances are not sufficiently improved.

Further, as a technique for improving discoloration and the number of foreign substances, a method of adding a plasticizer such as mineral oil to polyphenylene ether to lower the processing temperature of melt extrusion has been carried out for a long time. In a molded article obtained by using an ether resin, discoloration and the number of foreign substances are reduced, but heat resistance and mechanical properties are reduced. Therefore, the functionalized polyphenylene ether resin obtained by the prior art has not sufficiently responded to the demands of the industry because the surface appearance and the balance between heat resistance and mechanical properties are insufficient.

[0007]

An object of the present invention is to provide a sheet or film obtained by using a functionalized polyphenylene ether resin, which has sufficient functionalities such as coating adhesion and reduces discoloration and the number of foreign substances. Improves the surface appearance, and furthermore has a good balance of heat resistance and mechanical properties.
It is an object of the present invention to provide a sheet and a film of a functionalized polyphenylene ether resin which sufficiently satisfies the demands of the industry.

[0008]

Means for Solving the Problems As a result of repeated studies to achieve the above object, the present inventor has sufficient functionalities,
Sheets and films of functionalized polyphenylene ether resin with excellent surface appearance and excellent heat resistance and mechanical properties were completed.

That is, the present invention provides: (A) 100 parts by weight of polyphenylene ether;
(B) 0.01 to 10.0 parts by weight of a conjugated non-aromatic diene compound, a dienophile compound having one dienophile group, or a modifier selected from these dienes or dienophile compound precursors was added. Reacting the mixture at a reaction temperature not lower than room temperature and not higher than the melting point of the polyphenylene ether (A) to obtain a sheet and a film comprising the (C) functionalized polyphenylene ether resin,

[0010] 2. 0.1 to 99.9% by weight of (C) the functionalized polyphenylene ether resin and 0.1 to 99.9% by weight of (A) the polyphenylene ether according to the above 1.
2. Sheets and films consisting of (C) 0.1 to 99.9% by weight of the functionalized polyphenylene ether resin, (A) 0 to 99.8% by weight of the polyphenylene ether and (D) 0.1 to 99.9% by weight of the polystyrene resin. Sheets and films, comprising

4. (C) 0.1 to 99.9% by weight of the functionalized polyphenylene ether resin described in 1, (A) 0 to 99.8% by weight of the polyphenylene ether, (D) 0 to 99.8% by weight of the polystyrene resin, and ( E) sheets and films comprising 0.1 to 99.9% by weight of a polyamide resin,

5. (C) 0.1 to 99.9% by weight of a functionalized polyphenylene ether resin described in 1, (A) 0 to 99.8% by weight of a polyphenylene ether, (D) 0 to 99.8% by weight of a polystyrene resin, ( E) a sheet and a film comprising 0 to 99.8% by weight of a polyamide resin and (F) 0.1 to 50% by weight of an aromatic vinyl compound-conjugated diene compound copolymer and / or a hydrogenated product thereof;

6. (C) 0.1 to 99.9% by weight of a functionalized polyphenylene ether resin described in 1, (A) 0 to 99.8% by weight of a polyphenylene ether, (D) 0 to 99.8% by weight of a polystyrene resin, ( E) 0 to 99.8% by weight of a polyamide resin, (F) 0 to 50% by weight of an aromatic vinyl compound-conjugated diene compound copolymer and / or a hydrogenated product thereof, and a general formula (Formula 1) G)
Sheets and films consisting of 0.1 to 30% by weight of a phosphate compound,

7. (A) Polyphenylene ether is
7. The sheet and film according to any one of the above items 1 to 6, which is a polyphenylene ether having a melting point of 240 ° C. to 260 ° C. in the form of a powder obtained by precipitation from a solution. When formed into a film having a thickness of 0.1 to 0.5 mm and the number of foreign substances is measured, the number of foreign substances in 0.25 square meters of the film is 20 or less, any of the above 1 to 7, And sheets and films described in the above.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. The polyphenylene ether (A) of the present invention has a repeating unit structure of the formula (2), and has a reduced viscosity (0.5 g).
/ Dl, chloroform solution, measured at 30 ° C) is 0.15
1.0 dl / g, more preferably 0.20 to 1.0 dl / g.
It is a polymer or copolymer in the range of 0.70 dl / g.

[0016]

Embedded image (R ₅ and R ₈ are each independently hydrogen, primary or secondary lower alkyl, phenyl, aminoalkyl,
Represents hydrocarbonoxy. R ₆ and R ₇ each independently represent hydrogen, primary or secondary lower alkyl, or phenyl. )

Specific examples of the polyphenylene ether include poly (2,6-dimethyl-1,4-phenylene ether) and poly (2-methyl-6-ethyl-1,4
-Phenylene ether), poly (2-methyl-6-phenyl-1,4-phenylene ether), poly (2,6-
Dichloro-1,4-phenylene ether); and 2,6-dimethylphenol and other phenols (for example, 2,3,6-trimethylphenol and 2
-Methyl-6-butylphenol) and polyphenylene ether copolymers. Among them, poly (2,6-dimethyl-1,4-phenylene ether) and a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol are preferable, and poly (2,6-dimethylphenol) is most preferable. Dimethyl-1,4-phenylene ether).

As an example of a method for producing the polyphenylene ether used in the present invention, there is a method described in US Pat. No. 3,308,874 in which a complex of a cuprous salt and an amine is used as a catalyst to oxidatively polymerize 2,6-xylenol. is there. U.S. Pat. Nos. 3,306,875 and 325,735
No. 7 and No. 3257358, Japanese Patent Publication No. 52
The methods described in JP-A-17880 and JP-A-50-51197 and JP-A-63-152628 are also preferable as the method for producing polyphenylene ether.

The terminal structure of the polyphenylene ether of the present invention is preferably a structure of the following (formula 3).

Embedded image [Wherein, R ₅ , R ₆ , R ₇ , and R ₈ are each the same as in the above (Formula 2)
Is defined in the same manner as R ₅ , R ₆ , R ₇ and R ₈ . ]

The terminal structure of the polyphenylene ether of the present invention more preferably has the following formula (formula 3 ').

Embedded image [In the formula, R ₉ and R ₉ ′ represent hydrogen or an alkyl group. ]

As the polyphenylene ether (A) of the present invention, a crystalline polyphenylene ether having a melting point is used. References showing the relationship between crystalline polyphenylene ether and its melting point include, for example, Journal of
Polymer Science, Part A-2
(6) 1141-1148 (1968), Euro
pean Polymer Journal (9) 29
3-300 (1973), Polymer (19)
81-84 (1978).

In the present invention, the melting point of the polyphenylene ether (A) is measured by a differential scanning calorimeter (DSC) for the polyphenylene ether in a temperature-heat flow graph obtained when the temperature is increased at 20 ° C./min. It is defined by the peak top temperature of the observed peak, and when there are multiple peak top temperatures, it is defined by the highest temperature among them. The polyphenylene ether (A) of the present invention is a powder obtained by precipitation from a solution and has a melting point of 240.
It is preferably a polyphenylene ether having a temperature of from about 200C to about 260C. Further, this powder preferably has a heat of fusion (ΔH) obtained from a peak in DSC measurement of 2 J / g or more.

In the polyphenylene ether of the present invention, an organic solvent derived from the polymerization solvent may remain in an amount of 5% by weight or less. It is difficult to completely remove the organic solvent caused by these polymerization solvents in a drying step after polymerization,
Usually, it remains in the range of several hundred ppm to several%. The modifier (B) of the present invention is a modifier selected from a conjugated non-aromatic diene compound, a dienophile compound having one dienophile group, or a precursor of these dienes or dienophile compounds.

Among these modifiers, a double bond and at least one of a carboxyl group, an acyl oxide group, an imino group, an imide group, a hydroxyl group and a glycidyl group are preferred.
Preferably, it is a compound having a species in its molecular structure. Among them, maleic anhydride, maleic acid, fumaric acid, phenylmaleimide, itaconic acid, glycidyl methacrylate, and glycidyl acrylate are extremely preferable. The (C) functionalized polyphenylene ether resin of the present invention is obtained by reacting (A) polyphenylene ether with (B) a modifying agent by a specific production method.

The functionalized polyphenylene ether resin (C) of the present invention is used as a raw material for functionalizing the polyphenylene ether (A).
The polyphenylene ether is obtained by reacting with the modifier (B) at a reaction temperature equal to or lower than the melting point of the polyphenylene ether (A), that is, in a solid state of the polyphenylene ether (A). In the production of the (C) functionalized polyphenylene ether resin of the present invention, the temperature at which the mixture of (A) the polyphenylene ether and the (B) modifier is reacted is preferably in the range of room temperature to 240 ° C,
It is very preferable that the temperature is in the range of 100 ° C to 220 ° C. In the present invention, room temperature is 27 ° C.

If the temperature at which the mixture of (A) the polyphenylene ether and the (B) modifier is reacted at a temperature lower than room temperature, the (A) polyphenylene ether and the (B) modifier do not react sufficiently, and when the temperature exceeds 240 ° C. A) It is not preferable because polyphenylene ether is not melted. (C) of the present invention
In the production method of the functionalized polyphenylene ether resin, the modifier (B) is used in an amount of 0.01 to 10.0 parts by weight, preferably 0.1 to 5.0 parts by weight, based on 100 parts by weight of the polyphenylene ether (A). , More preferably 0.5 to
It reacts by mixing 3.0 parts by weight. (B) The modifier is 0.0
If the amount is less than 1 part by weight, the amount of the functional group is insufficient,
If the amount exceeds 0.0 parts by weight, the polymer is undesirably attached to a reaction tank or a pipe.

The mixing method of (A) polyphenylene ether and (B) modifier is as follows: 1) dry blending, 2) impregnation and mixing of (B) liquefied modifier, and 3) (B) modifier such as acetone. A method of dissolving in an organic solvent, impregnating and mixing, or charging each into a reaction tank and mixing in a reaction tank is preferable.
When (B) the modifier is dissolved in an organic solvent and (A) polyphenylene ether is impregnated and mixed, 10 parts by weight or less, more preferably 5 parts by weight or less of 100 parts by weight of (A) polyphenylene ether is used. Solvents can be used. Preferred organic solvents are methyl alcohol, ethyl alcohol, acetone, dimethyl ketone,
Methyl ethyl ketone, n-hexane, cyclohexane,
Examples thereof include tetrahydrofuran and the like, and among them, methyl alcohol and acetone are more preferable. However, the present invention is not limited to the above, and any mixing method may be used as long as the method does not impair the object of the present invention.

In the present invention, the reaction pressure is from 0 to 2 MPa.
And more preferably in the range of 0 to 1 MPa. In the method for producing the functionalized polyphenylene ether resin (C) of the present invention, the production is preferably carried out using a Henschel mixer, a paddle dryer, and a surface modification device as a reactor. However, the method for producing (C) the functionalized polyphenylene ether resin of the present invention is not limited to the above.

The functionalized polyphenylene ether resin (C) of the present invention is different from the conventional production method by melt kneading, because it reacts in a solid state and does not generate shear heat during melt kneading. Since it has no discoloration or foreign matter, it has an excellent surface appearance. Furthermore, since the functionalized polyphenylene ether resin (C) of the present invention does not use a plasticizer in the production, the original heat resistance and mechanical properties of the polyphenylene ether are maintained.

Accordingly, since the functionalized polyphenylene ether resin (C) of the present invention can be obtained by a specific production method, it has sufficient functionalities, has an excellent surface appearance, and has excellent heat resistance and mechanical properties. The sheet or film obtained from the functionalized polyphenylene ether resin (C) has sufficient coating adhesion and metal adhesion, and has good surface appearance, heat resistance, and mechanical properties. It can be provided to various industrial fields that sufficiently meet the needs of the world.

The functionalized polyphenylene ether resin (C) of the present invention is preferably used in an amount of 0.1 to 100% by weight, more preferably 0.5 to 100% by weight, in the sheet or film of the functionalized polyphenylene ether resin. It is. (C) 0.1% of the functionalized polyphenylene ether resin
If the amount is less than% by weight, functionalities such as coating adhesion and adhesion to metal when used as a sheet or a film are insufficient, which is not preferable. The (C) functionalized polyphenylene ether resin of the present invention can be produced by adding a reaction auxiliary such as a radical initiator.

A desired additive may be added to the polyphenylene ether resin (A) or the functionalized polyphenylene ether resin (C) of the present invention according to the purpose. Examples of additives used include heat stabilizers, antioxidants, UV absorbers, surfactants, lubricants, fillers, polymer additives, dialkyl peroxides, diacyl peroxides, peroxycarbonates, hydroperoxides, And peroxyketal.

The (D) polystyrene resin of the present invention is:
It is a polymer obtained by polymerizing a styrene compound or a compound copolymerizable with the styrene compound in the presence or absence of a rubbery polymer. Specific examples of the styrene compound include styrene, α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, p-methylstyrene,
p-tert-butylstyrene, p-aminostyrene,
Ethyl styrene and the like may be mentioned, and a mixture thereof may be used. Further, as the compound copolymerizable with the styrene compound, methyl methacrylate, methacrylic acid esters such as ethyl methacrylate, acrylonitrile, unsaturated nitrile compounds such as methacrylonitrile,
Acid anhydrides such as maleic anhydride may be mentioned, and may be used in combination with the styrene compound.

Examples of the rubbery polymer include a conjugated diene rubber, a copolymer of a conjugated diene and an aromatic vinyl compound or a hydrogenated product thereof, an ethylene-propylene copolymer rubber, and an ethylene-propylene-diene rubber. Or a mixture thereof. further,
Examples of the conjugated diene rubber include a chromium compound or an organometallic compound (eg, trialkylaluminum) adsorbed on an inorganic support and a transition metal compound (eg, a halogenide, particularly titanium chloride, titanium iodide or lithium halogenide). Using a catalyst containing a reaction product, butadiene is produced by stereoregular polymerization in an inert hydrocarbon solution. At least 50% by weight of 1,4-cis bonds and 10% by weight of 1,2-vinyl bonds The following may be used. Further, a partially hydrogenated conjugated diene rubber in which unsaturated bonds are reduced by hydrogenating a conjugated diene rubber may be used.

Further, a core-shell type high impact polystyrene resin in which polystyrene particles encapsulated in rubber are dispersed in a polystyrene resin matrix can be suitably used in the present invention. Of course, these conjugated diene rubbers may be a mixture of two or more. The method for producing the polystyrene resin (D) of the present invention is not limited, and any of bulk polymerization, solution polymerization, emulsion polymerization, and suspension polymerization well known to those skilled in the art may be used.

The (E) polyamide resin of the present invention has an amide bond {—NH—C (＝ O)} in the polymer main chain. Generally, the polyamide resin is obtained by ring-opening polymerization of lactams, polycondensation of diamine and dicarboxylic acid, polycondensation of aminocarboxylic acid, and the like, but is not limited thereto.

The above-mentioned diamines are roughly classified into aliphatic, alicyclic and aromatic diamines. Specific examples thereof include tetramethylene diamine, hexamethylene diamine, undecamethylene diamine, dodecamethylene diamine, tridecamethylene diamine, and 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 5-methylnanomethylenediamine,
Examples thereof include 1,3-bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane, m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, and p-xylylenediamine.

The dicarboxylic acids are roughly classified into aliphatic,
Alicyclic and aromatic dicarboxylic acids are mentioned, and specific examples are adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 1,1,3-tridecandioic acid,
1,3-cyclohexanedicarboxylic acid, terephthalic acid,
Examples include isophthalic acid, naphthalenedicarboxylic acid, and dimer acid. As lactams, specifically, ε-
Caprolactam, enantholactam, ω-laurolactam and the like.

Examples of the aminocarboxylic acid include ε-aminocaproic acid, 7-aminoheptanoic acid, 8
-Aminooctanoic acid, 9-aminonanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, 13-aminotridecanoic acid and the like. In the present invention,
Any of these lactams, diamines, dicarboxylic acids, and ω-aminocarboxylic acids may be used alone or in the form of a mixture of two or more copolymerized polyamides.

Also, those obtained by polymerizing these lactams, diamines, dicarboxylic acids and ω-aminocarboxylic acids to a low molecular weight oligomer stage in a polymerization reactor and increasing the molecular weight by an extruder or the like can be suitably used. it can.

Particularly useful polyamide resins useful in the present invention are polyamide 6, polyamide 6,
6, Polyamide 4, 6, Polyamide 11, Polyamide 1
2, polyamide 6,10, polyamide 6,12, polyamide 6 / 6,6, polyamide 6 / 6,12, polyamide 6 / MXD (m-xylylenediamine), polyamide 6, T, polyamide 6, I, polyamide 6 / 6, T, polyamide 6/6, I, polyamide 6,6 / 6, T, polyamide 6,6 / 6, I, polyamide 6/6, T / 6
I, polyamide 6,6 / 6, T / 6, I, polyamide 6
/ 12/6, T, polyamide 6,6 / 12/6, T, polyamide 6/12/6, I, polyamide 6,6 / 12 /
And polyamides obtained by copolymerizing a plurality of polyamides with an extruder or the like.

The preferred number average molecular weight of the polyamide resin (E) of the present invention is from 5,000 to 100,000, more preferably from 10,000 to 30,000. The polyamide resin in the present invention may be a mixture of a plurality of polyamide resins having different molecular weights. For example, a low molecular weight polyamide having a number average molecular weight of 10,000 or less,
A mixture of a high-molecular-weight polyamide having a number average molecular weight of 10,000 or less;
A general polyamide mixture of about 00 or the like may be used, but the present invention is not limited thereto.

(E) The terminal group of the polyamide resin participates in the reaction with the functionalized polyphenylene ether resin. The polyamide resin usually has an amino group and a carboxyl group as a terminal group. Generally, when the carboxyl group concentration exceeds the amino group concentration, the impact resistance is reduced and the fluidity is improved. Conversely, when the amino group concentration exceeds the carboxyl group concentration, the impact resistance is improved and the fluidity is reduced. These preferred ratios are amino group / carboxyl group ratios of 9/1 to 1/1.
9 It is more preferably from 8/2 to 1/9, and still more preferably from 6/4 to 1/9. Further, the concentration of the terminal amino group is preferably at least 10 meq / kg. More preferably, it is 30 meq / kg or more.

The method for adjusting the terminal groups of these polyamide resins may be a known method well known to those skilled in the art. For example, addition of a diamine or a dicarboxylic acid, addition of a monocarboxylic acid, or the like during polymerization of a polyamide resin may be mentioned. For the purpose of improving the heat stability of the polyamide resin, a metal stabilizer well known to those skilled in the art can also be used. Specific examples of the metal-based stabilizer include C
Examples thereof include uI, CuCl ₂ , copper acetate, potassium iodide, and cerium stearate, and these may be used in combination. The preferred amount of the metal-based stabilizer is 0.001 to 1 part by weight based on 100 parts by weight of the polyamide resin.

In the present invention, the aromatic vinyl compound-conjugated diene compound copolymer (F) in the aromatic vinyl compound-conjugated diene compound copolymer and / or a hydrogenated product thereof is a conjugated diene compound and an aromatic vinyl compound. It is a copolymer with an aromatic vinyl compound. Specific examples of the conjugated diene compound include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, and 1,3-butadiene.
Pentadiene may be used, and two or more of these may be used in combination. Among these, 1,3-butadiene and 2-methyl-1,3-butadiene are preferable, and 1,3-butadiene is more preferable.
Butadiene is particularly preferred.

Specific examples of the aromatic vinyl compound include styrene, p-methylstyrene, α-methylstyrene, vinylxylene, vinyltoluene, vinylnaphthalene, divinylbenzene, bromostyrene, and chlorostyrene. Combinations of the above are also possible. Of these, styrene, α-methylstyrene, vinyl xylene, and vinyl toluene are preferred, and styrene is particularly preferred.

The conjugated diene compound-aromatic vinyl compound copolymer obtained by copolymerizing these unsaturated compounds is conjugated diene compound / aromatic vinyl compound = 5-95 /
The conjugated diene compound / aromatic vinyl compound is preferably obtained in the range of 95 to 5% by weight.
/ 40-5% by weight, more preferably 40-95 / 60-
A range of 5% by weight is preferred.

The hydrogenated product of the aromatic vinyl compound-conjugated diene compound copolymer refers to the hydrogenated product of the aromatic vinyl compound-conjugated diene compound copolymer in which the aliphatic unsaturated group in the conjugated diene compound is hydrogenated. It has been reduced by The hydrogenated product of the conjugated diene compound-aromatic vinyl compound copolymer that can be used in the present invention is the aliphatic conjugated diene compound-aromatic vinyl compound copolymer having the above-mentioned structure, which is derived from the aliphatic conjugated diene compound. At least 50%, preferably at least 80%, of the saturated groups are hydrogenated. Moreover, 25% or less of the unsaturated bond of the aromatic ring derived from the aromatic vinyl compound may be hydrogenated. The hydrogenation treatment method is described in, for example,
8704, JP-B-43-6636, JP-B-46-20814 or JP-B-63-5401.
No., etc.

The bonding form of the conjugated diene compound-aromatic vinyl compound copolymer and the hydrogenated product of the conjugated diene compound-aromatic vinyl compound copolymer is based on the block copolymer (conjugated diene compound-aromatic compound). Hydrogenated products of a vinyl compound block copolymer and a conjugated diene compound-aromatic vinyl compound block copolymer) are preferred. The conjugated diene compound-aromatic vinyl compound block copolymer referred to herein is an aromatic vinyl having at least one chain block “a” derived from an aromatic vinyl compound and at least one chain block “b” derived from a conjugated diene compound. It is a compound-conjugated diene compound-based copolymer.

The hydrogenated product of the conjugated diene compound-aromatic vinyl compound block copolymer as used herein means the conjugated diene compound-aromatic compound having at least one of each of the above-mentioned chain blocks "a" and "b". The block copolymer is a conjugated diene compound-aromatic vinyl compound-based copolymer in which aliphatic unsaturated groups mainly in the part of the chain block “b” of the aromatic vinyl compound block copolymer are reduced by hydrogenation. The united structures are diblock (ab) and triblock (ab-) which form a linear structure.
a, baab), tetrablock (abba-
b), or the total number of blocks a and b may be 5 or more, and a branched structure, that is, a so-called radial teleblock type structure may be used. Among these, diblock, triblock and tetrablock structures are preferable, and triblock and tetrablock are particularly preferable.

The distribution of the monomer component is not particularly limited, and may be uniform or non-uniform, or may be a tapered shape in which the concentration of the monomer component changes along the molecular chain. Further, all or some of the copolymers used as the component (F) may be modified products of unsaturated carboxylic acids and / or derivatives thereof. Modified products of maleic anhydride and methacrylic acid esters may be mentioned.

In the present invention, the conjugated diene compound-aromatic vinyl compound copolymer and the hydrogenated product thereof which can be used as the component (F) are two types of copolymers having the above-mentioned structure. A mixture of the above may be used. The (G) phosphate compound of the present invention has the general formula (Formula 1)
It is represented by

[0053]

Embedded image

(Q1, Q2, Q3, and Q4 each independently represent an alkyl group having 1 to 6 carbon atoms. R1 and R2 each represent a methyl group, and R3 and R4 each independently represent a methyl group or hydrogen.
Represents an integer of 1 or more. n1 and n2 independently represent an integer of 0 to 2. m1, m2, m3 and m4 each independently represent an integer of 0 to 3. In the general formula (Formula 1), n1 and n2 are 0, and R3 and R4
Is preferably a methyl group.

In the general formula (formula 1), m1 and m
2, m3 and m4 are 0, that is, there is no substitution of an alkyl group to a terminal phenyl group, or Q1, Q2, Q
Most preferably, 3, Q4 is a methyl group, that is, the methyl group to the terminal phenyl group is substituted. N in the general formula (Formula 1) is an integer of 1 or more, and the preferable range of n is 1 to 10. The (G) phosphate compound may be a mixture of n-mers.

The (G) phosphate compound of the present invention is
It has a bonding structure with a specific bifunctional phenol and a terminal structure with a specific monofunctional phenol. As a bifunctional phenol, 2,2-bis (4-hydroxyphenyl)
Propane [commonly known as bisphenol A], 2,2-bis (4
Bisphenols such as -hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5-dimethylphenyl) methane and 1,1-bis (4-hydroxyphenyl) ethane Among them, bisphenol A is preferable.

As the monofunctional phenol, unsubstituted phenol, monoalkylphenol, dialkylphenol and trialkylphenol can be used alone or as a mixture of two or more. Particularly, phenol, cresol, dimethylphenol (mixed xylenol), 2,6-dimethylphenol, and trimethylphenol are preferable.
(G) The phosphate compound can be obtained by reacting the above-mentioned bifunctional phenols and monofunctional phenols with phosphorus oxychloride.

The (G) phosphate ester used in the present invention is
Other phosphoric esters generally used within a range not to impair the effects of the invention, for example, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, dicresyl phenyl phosphate, hydroxyphenyl diphenyl phosphate And the like, a compound obtained by modifying these with various substituents, various condensation type phosphate ester compounds, and the like. Of course, these mixtures may be contained.

The (G) phosphate compound of the present invention is
Low volatility and excellent thermal stability. For example, in the case of a low-molecular-weight phosphate compound represented by triphenyl phosphate, the phosphate compound is volatilized at the time of forming a film or sheet, causing a problem that the surface of the film or sheet is roughened and the surface appearance is deteriorated. Further, even among the polyphosphate ester compounds, those having low thermal stability may react with the polyphenylene ether-based resin to cause a kind of crosslinking reaction called gelation. In order to obtain a good surface appearance of a film or sheet, the phosphate compound of the present invention is extremely preferable.

The resin component constituting the sheet and film of the present invention preferably comprises (C) a functionalized polyphenylene ether resin in an amount of 0.1 to 100% by weight.
If it is less than 0.1% by weight, sufficient functionality may not be obtained, which is not preferable. (A), (D),
Each component of (E), (F) and (G) is used in an appropriate amount according to the purpose. (A) The appropriate amount of polyphenylene ether is (C) 0.1% of the functionalized polyphenylene ether resin.
0.1-99.9% by weight with respect to 99.9% by weight, and (D) a suitable amount of the polystyrene resin is (C) or a mixture of (C) and (A) 99.9-0. .1% by weight,
(D) 0.1 to 99.9% by weight of a polystyrene resin.

Next, an appropriate amount of the (E) polyamide resin is as follows:
(C) or 0.1 to 99.9% by weight of a mixture of (C) and one or more selected from (A) and (D);
The polyamide resin is 0.1 to 99.9% by weight, more preferably 10 to 75% by weight of (C) or a mixture of (C) and one or more kinds selected from (A) and (D).
And (E) 25 to 90% by weight of a polyamide resin.

Next, the aromatic vinyl compound (F)
An appropriate amount of the conjugated diene compound copolymer and / or a hydrogenated product thereof is (C) or (C) and (A), (D),
0.1 to 99.9% by weight of a mixture of at least one selected from (E) and (G), and an aromatic vinyl compound-conjugated diene compound copolymer of component (F) and / or hydrogenation thereof 0.1 to 50% by weight, and preferably 0.1 to 50% by weight.
It is 5 to 20% by weight, more preferably 1 to 10% by weight.

Further, an appropriate amount of the (G) phosphate ester is as follows:
(C) or (C) and (A), (D), (E),
(F) a mixture of one or more kinds selected from 0.1 to 0.1
99.9% by weight and (G) phosphate ester 0.1 to 30
%, Preferably 0.5 to 20 parts by weight, more preferably 1 to 15 parts by weight. Desirable thickness of the sheet and film of the present invention is 0.01 to 10 mm. It is preferably from 0.1 to 5 mm, more preferably from 0.1 to 3 mm.

The method of mixing the components of the sheet and the film according to the present invention is a method of dry blending the components and directly adding them to a film extruder or a sheet extruder, a single screw or a twin extruder.
A method of melt kneading in advance with a screw extruder is considered,
Furthermore, a method in which only the components (C), (A), and (D) are melt-kneaded in advance and the other components are added when kneading with a film extruder or a sheet extruder can be considered. Any method may be used as long as the purpose is not impaired.

The sheets and films of the present invention may be blended with other thermoplastic resins in addition to the above components or laminated with films or sheets made of other thermoplastic resins, as long as the characteristics are not impaired. I do not care. Examples of the thermoplastic resin include, for example, polystyrene, acrylonitrile-styrene copolymer, polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-
General-purpose plastics such as propylene-diene terpolymer, polyvinyl chloride, polyvinylidene chloride, polymethyl methacrylate, polyacetal, polyamide (polyamide 6, polyamide 6,6, polyamide 12, polyamide 11, polyamide 4,6 Engineering plastics, such as polybutylene terephthalate, polycarbonate, polyethylene terephthalate, polyphenylene ether resin, etc.

Other resins (fluorine resin, silicon resin, etc.) such as super engineering plastics such as polyimide, polyarylate, polyetherimide, polyphenylene sulfide, polyetherketone, polyetheretherketone, polysulfone, and polyethersulfone. And the like, and a mixture of two or more of these may be used. Also, a multilayer lamination using two or more of these resins may be used.

Further, the sheet and film of the present invention may contain, in addition to the above components, known inorganic and organic fillers and reinforcing materials (glass fiber, carbon fiber, carbon fiber, etc.) as long as their characteristics are not impaired. Diatomaceous earth, whisker, mica, talc, calcium carbonate, potassium titanate, zinc sulfide, zinc oxide, wollastonite, etc.). These fillers and reinforcing materials may be granular or fibrous. In addition, various oils (mineral oil, silicone oil, etc.), other flame retardants (other phosphate esters, halogenated flame retardants such as brominated polystyrene, etc.), flame retardant aids, antioxidants, ultraviolet absorbers, Plasticizers, antistatic agents, various colorants, fragrances, lubricants,
Additives such as a release agent and a nucleating agent can be added for use. Of course, mixtures thereof are also useful.

The sheet and film of the present invention can be used for ceiling materials, wall materials, floor materials of automobiles and trains, outer plates of home appliances and OA equipment, earth and wood (ceiling materials, wall materials, floors of general buildings and factories, etc.). Materials), display materials and the like. Moreover, it can also be used by laminating it with other films, sheets, foamed sheets and the like. Specific examples of film lamination include rigidity, strength, and dimensional stability of foam materials used for interior materials such as ceilings and walls of automobiles and trains and rear shelves of automobiles to ensure heat insulation and sound absorption and insulation. In order to improve the quality, a material laminated on one side or both sides of the foam may be used.

The sheets and films of the present invention can be used by laminating them on other films, plate-like molded products, foamed sheets and the like. Lamination to other films or plate-like molded articles, foamed sheets, etc., a method of laminating both with an adhesive, a method of heat bonding, and the like, but a method of heat bonding is preferable, and a method of bonding with a hot roll, A method of in-line lamination immediately after extrusion of a film or sheet, a co-extrusion lamination method using a multilayer extrusion die, and the like can be particularly preferably used.

Hereinafter, embodiments of the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following embodiments. In the examples and comparative examples, the following (A) polyphenylene ether was used. A-1: Poly (2,6-dimethyl-1,4 having a reduced viscosity of 0.54 obtained by oxidative polymerization of 2,6-dimethylphenol.
-Phenylene ether), and the melting point determined by DSC was 250 ° C.

In the examples, the following (C) functionalized polyphenylene ether resin was used. C-1: 100 parts by weight of polyphenylene ether of A-1 and 2 parts by weight of (B) modifier (maleic anhydride) were placed in a jacket-coolable FM500 type Henschel mixer manufactured by Mitsui Mining Co., Ltd., and the stirring blade was rotated at high speed. Spin and heat the contents to 190 ° C. over 50 minutes due to shear heat. After the jacket temperature reached 190 ° C., cold water was passed through the jacket to cool it. The mixture was discharged from a Henschel mixer to obtain a functionalized polyphenylene ether resin.

In order to measure the addition rate of maleic anhydride,
Unreacted maleic anhydride is washed away with acetone,
A film was obtained by a press molding machine set at 280 ° C,
Infrared spectroscopy was performed. As a result of infrared spectroscopy, 1790
In cm ⁻¹ , a peak derived from maleic anhydride added to polyphenylene ether was observed, and when maleic anhydride was quantified by a calibration curve created in comparison with a peak derived from polyphenylene ether at 2735 cm ⁻¹ , maleic anhydride was added. The amount was 1.54% by weight.

Further, when a 5 wt% chloroform solution of the functionalized polyphenylene ether resin was used and the amount of unreacted maleic anhydride was determined by gas chromatography, it was 0.22 wt% in the functionalized polyphenylene ether resin. In the comparative example, the following functionalized polyphenylene ether resin obtained according to the prior art was used in place of the functionalized polyphenylene ether resin (C). C′-1: 100 parts by weight of polyphenylene ether A-1 and 2 parts by weight of a modifier (maleic anhydride) (B) were dry-blended, and a co-rotating twin-screw extruder set at 340 ° C. [Z
SK-25: manufactured by Werner & Faudler Co., Ltd.], melt-kneaded, and the strands coming out of the small holes of the dies were cooled by passing through a water tank, and then cut to obtain pellets.

To determine the addition rate of maleic anhydride,
After making the pellet a 10 wt% chloroform solution,
Precipitated by filtration and filtered. With acetone
Unreacted maleic anhydride is washed off, dried, and dried.
Film obtained by a press molding machine set to
Light measurements were taken. As a result of infrared spectroscopy, 1790 cm ^-1
And maleic anhydride added to polyphenylene ether
An acid-derived peak was observed at 2735 cm^-1Polyfe
Calibration curve created by comparing peaks derived from nylene ether
The amount of maleic anhydride is determined by
The addition amount was 1.63% by weight.

Further, the unreacted maleic anhydride was quantified using a gas chromatograph as a 5 wt% chloroform solution of the pellets, and found to be 0.18 wt% in the functionalized polyphenylene ether resin. In the examples and comparative examples, the following two types of polystyrene resin (D) were used. D-1: polystyrene 685 [manufactured by A & M Styrene Co., Ltd.] D-2: 9 parts of polybutadiene having 98% of cis 1,4 bonds
%, A rubber particle size of 1.5 μm, and a reduced polystyrene of 0.82 as measured in toluene at 30 ° C.
dl / g of rubber-modified impact-resistant polystyrene resin.

In the examples and comparative examples, the following polyamide resin (E) was used. E-1: Polyamide 6,6 [Leona 1300S manufactured by Asahi Kasei Corporation] In Examples and Comparative Examples, (F) hydrogenated aromatic vinyl compound-conjugated diene compound block copolymer, hydrogenated aromatic The following were used as modified products of the group III vinyl compound-conjugated diene compound block copolymer. F-1: a polystyrene-hydrogenated polybutadiene-polystyrene block copolymer obtained by the following method.

In a 100-liter autoclave equipped with a stirrer and a jacket replaced with nitrogen, 66.2 cyclohexane was added.
One liter and 1.62 kg of styrene were charged and heated to 70 ° C. while stirring. Furthermore, sec-butyl lithium 1
0.68 g and tetrahydrofuran as a vinylating agent were added, and polymerized at 70 ° C. for 60 minutes. Thereafter, 6.05 kg of butadiene was supplied to an autoclave and polymerized at 70 ° C. for 60 minutes. After polymerizing butadiene for a predetermined time, 1.62 kg of styrene was further supplied to the autoclave, and 70 ° C.
The polymerization was continued for 60 minutes with a polystyrene-butadiene-polystyrene structure.
% By weight, number average molecular weight of polystyrene block segment 28,000, molecular weight distribution of entire polymer 1.03,
A block copolymer having 36% of 1,2 bonds in the butadiene segment was obtained. The polystyrene-butadiene-polystyrene block copolymer obtained here was further converted to
A hydrogenation reaction was carried out in the same manner as in Examples 1 to 12 of JP-A-5401 to obtain a polystyrene-hydrogenated polybutadiene-polystyrene structure and a hydrogenation rate of 99.
A 9% hydrogenated block copolymer was obtained.

In Examples and Comparative Examples, the following compounds were used as the (G) phosphate compound. G-1: bisphenol A-polycresyl phosphate: Chemical formula (Formula 4) (a mixture of n = 1 to 3).

[0079]

Embedded image

[0080]

Examples 1 to 8 Each component was dry blended in the proportions shown in Table 1 and a co-rotating twin screw extruder [ZS set at 300 ° C.]
K-25: manufactured by Werner & Faudler Co., Ltd.], melt-kneaded, and the strands coming out of the small holes of the dies were cooled by passing through a water tank, and then cut to obtain pellets. The obtained pellets were supplied to a 30 mmφ single-screw film extruder, and the width 5
Extruded into a 0 cm film. When the thickness of the film was measured, it was about 0.3 mm. Further, the obtained pellet was supplied to a 30 mmφ single-screw sheet extruder, and the width was 30 c.
m extruded into a sheet. When the thickness of the sheet was measured, it was about 5 mm.

For the surface appearance, the extruded film having a width of 50 cm was cut out at a length of 50 cm, and the number of black foreign substances was determined by visual inspection. The number of foreign matters was evaluated as 4 on a scale of 5 or less, ◎, 6 to 20 or less, 、 ２, 21 to 50, Δ, and 51 or more. For the evaluation of the functionality, the extruded sheet having a width of 30 cm was cut out at a length of 30 cm, coated with a commercially available urethane-based paint, and then 2 × 2 mm × 100 grids were attached to the center portion with a cutter knife. After a cellophane tape was stuck on the grid and sufficiently adhered, the cellophane tape was peeled off, and the coating adhesion was evaluated by ranking according to the number of grids peeled off. The number of peeling was 0: 、 １, 1 to 10: 、 １, 11 to 20: Δ, 21 to 100: x. As a result of the evaluation, the number of foreign substances was reduced and the coating adhesion was excellent.

[0082]

Comparative Examples 1 to 8 In place of the C-1 component in the examples, A-
Using one component, dry blend at the ratio in Table 2,
A co-rotating twin-screw extruder [ZSK-25:
Werner & Faudler Co., Ltd.]
The strands coming out of the small holes were passed through a water bath, cooled, and then cut to obtain pellets. 3 pellets obtained
It was supplied to a 0 mmφ single screw film extruder and extruded into a film having a width of 50 cm. When the thickness of the film was measured, it was about 0.3 mm.

Further, the obtained pellets were supplied to a 30 mmφ single screw sheet extruder and extruded into a sheet having a width of 30 cm. When the thickness of the sheet was measured, it was about 5 mm.
The surface appearance and the functionality were evaluated in the same manner as in the examples.
As a result of the evaluation, the number of foreign substances was larger than that of the examples, and the adhesion was extremely poor. In Comparative Example 5, peeling was observed in the molded sheet.

[0084]

Comparative Examples 9 to 16 In place of the component C-1 in the examples,
Using the C′-1 component, dry blending was performed at the ratio shown in Table 3 and a co-rotating twin-screw extruder [ZSK set at 300 ° C.]
-25: manufactured by Werner & Faudler Co., Ltd.] and melt-kneaded. The strands coming out of the small holes in the dies were passed through a water bath, cooled, and then cut to obtain pellets. The obtained pellets were supplied to a 30 mmφ single-screw film extruder, and the width was 50 mm.
cm of film. When the thickness of the film was measured, it was about 0.3 mm.

The obtained pellets were supplied to a 30 mmφ single screw sheet extruder and extruded into a sheet having a width of 30 cm. When the thickness of the sheet was measured, it was about 5 mm.
The surface appearance and the functionality were evaluated in the same manner as in the examples.
As a result of the evaluation, the number of foreign substances was remarkably larger than that of the examples.

[0086]

[Table 1]

[0087]

[Table 2]

[0088]

[Table 3]

[0089]

The sheet and film obtained by using the functionalized polyphenylene ether resin obtained by the present invention have sufficient functionalities such as coating adhesion and the like, and have a reduced surface by reducing discoloration and the number of foreign substances. It is possible to provide a sheet and a film which improve appearance, have a good balance between heat resistance and mechanical properties, and sufficiently satisfy the demands of the industry.

Continuation of the front page (51) Int.Cl. ⁷ Identification code FI Theme coat II (reference) C08L 53/02 C08L 53/02 71/00 71/00 Z Y 77/00 77/00 F term (reference) 4F071 AA12X AA22X AA23 AA51 AA54 AA55 AA75 AA78 AA84 AC15 AF58 AH04 AH07 AH12 BA01 BB06 BC01 BC10 BC12 4J002 BC01Y BC10Y BP01U CH06X CH07W CL01Z CL03Z CL05Z EW046 GG00 GM00 GN00 GQ00 4J005 AA26 BD00

Claims (8)

[Claims] 1. A compound selected from (A) 100 parts by weight of polyphenylene ether, (B) a conjugated non-aromatic diene compound, a dienophile compound having one dienophile group, or a precursor of these dienes or dienophile compounds. A sheet comprising the functionalized polyphenylene ether resin (C) obtained by reacting the mixture to which 0.01 to 10.0 parts by weight of the modifier has been added at a reaction temperature of not lower than room temperature and not higher than the melting point of the polyphenylene ether; the film. 2. The polyphenylene ether resin (C) according to claim 1, wherein the polyphenylene ether is 0.1 to 99.9% by weight and the polyphenylene ether (A) is 0.1 to 99.9% by weight.
Sheets and films comprising. 3. The polyphenylene ether resin (C) according to claim 1, 0.1 to 99.9% by weight, (A) 0 to 99.8% by weight of the polyphenylene ether and (D).
Sheets and films composed of 0.1 to 99.9% by weight of polystyrene resin. 4. The polyphenylene ether resin according to claim 1, wherein (C) the functionalized polyphenylene ether resin is 0.1 to 99.9% by weight, (A) the polyphenylene ether is 0 to 99.8% by weight, and (D) the polystyrene-based resin is 0. Sheets and films comprising 99.8% by weight and (E) 0.1 to 99.9% by weight of a polyamide resin. 5. The polyfunctional polyphenylene ether resin (C) according to claim 1, 0.1 to 99.9% by weight, (A) polyphenylene ether 0 to 99.8% by weight, and (D) polystyrene resin 0 to 5. A sheet comprising 99.8% by weight, (E) 0 to 99.8% by weight of a polyamide resin, and (F) 0.1 to 50% by weight of an aromatic vinyl compound-conjugated diene compound copolymer and / or a hydrogenated product thereof. And film. 6. The functionalized polyphenylene ether resin (C) according to claim 1, 0.1 to 99.9% by weight, (A) 0 to 99.8% by weight of polyphenylene ether, and (D) polystyrene resin 0 to 0%. 99.8% by weight, (E) polyamide resin 0 to 99.8% by weight, (F) aromatic vinyl compound
Sheets and films comprising a conjugated diene compound copolymer and / or a hydrogenated product thereof in an amount of 0 to 50% by weight and a phosphate ester compound (G) represented by the general formula (Formula 1) in an amount of 0.1 to 30% by weight. Embedded image (Where Q1, Q2, Q3 and Q4 each independently have 1 carbon atom)
To 6 represent an alkyl group. R1 and R2 represent a methyl group,
R3 and R4 independently represent a methyl group or hydrogen. n is 1
Represents the above integer. n1 and n2 independently represent an integer of 0 to 2. m1, m2, m3 and m4 each independently represent an integer of 0 to 3. ) 7. The polyphenylene ether (A) is a powder obtained by precipitation from a solution and has a melting point of 24.
The sheet and film according to any one of claims 1 to 6, wherein the sheet and the film are polyphenylene ether at 0 ° C to 260 ° C. 8. A film having a thickness of 0.1 to 0.5 mm and measuring the number of foreign matters, wherein the number of foreign matters in 0.25 square meters of the film is 20 or less. Item 8. The sheet and film according to any one of Items 1 to 7.