JP5257036B2 - Cellulose ester resin composition and sheet molded product using the same - Google Patents

Description

The present invention relates to a cellulose ester resin composition excellent in impact resistance and a sheet molded article using the same.

Cellulose ester resin has a unique texture and feel, is excellent in transparency, and a clear and deep color can be obtained by coloring. Moreover, since it is excellent in cutting workability and has toughness, it is used for medical instruments, sports equipment, glasses frames and cosmetics containers, displays, outdoor signs, printed sheets and the like.

Among the uses are furniture, building materials, and ball game boards such as pachinko, etc. The structure is often used as a decorative board in which thermoplastic resin, paper, and wood are bonded together. However, due to the difference in shrinkage between the thermoplastic resin and paper, wood, etc., there has often been a problem that warpage of the laminated sheet occurs.

Cellulose ester is similar to paper, veneer board, beech board plywood, etc., and its elasticity with respect to temperature and humidity is close. Cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, etc. are polymer materials synthesized based on cellulose. It is used as a decorative board in which a cellulose ester resin is molded into a sheet and paper, a veneer board, a beech board plywood and the like are bonded together, and as a base board decoration sheet for a game machine (Patent Documents 1 and 2).

Such a cellulose ester resin molded product is often colored by melting and kneading an inorganic pigment. However, when titanium dioxide is melt kneaded into the cellulose ester resin, the cellulose ester resin deteriorates due to the surface activity of the titanium dioxide, and the molded product has a resistance to resistance. There was a problem that the impact property was lowered. If the impact resistance of the molded product is reduced, for example, when a ball game board is created, if the nail is hit on the molded product, the molded product is broken, and the product cannot be created (Patent Documents 2 and 3). Patent Documents 1-3 did not describe or suggest an essential solution to the above problem.

Further, Patent Document 4 describes a cellulose ester resin containing titanium dioxide surface-treated with a phosphorus compound, but these promote the degradability of the cellulose ester resin and improve the impact resistance of the cellulose ester resin. It is not something that can be improved, but rather its solution.

Patent Document 5 relates to a treated inorganic solid and is intended to form a thick blend mixed masterbatch with polyethylene or polypropylene.

On the other hand, although patent document 6 is related with the molded article of a cellulose ester blend, there is no description to the subject which this application tends to solve.
JP 58-145446 A JP 2003-38743 A JP 2006-280850 A JP-A-8-157644 JP-A-8-176460 JP 2007-277582 A

An object of the present invention is to provide a cellulose ester resin composition that does not impair the original impact resistance of the cellulose ester resin even when titanium dioxide is melt-kneaded with the cellulose ester resin, a sheet molded product using the same, and an elastic material using the same. To provide a ball game board.

In other words, in practical sites, distortions may occur due to temperature and humidity differences between winter and summer, or between daytime and nighttime, peeling from the base material, or cracks may occur. The purpose is to eliminate the adhesion to the nail and the generation of cracks from that area.

1st invention of this invention is 40-99.9 weight% of cellulose ester resin chosen at least 1 or more from the group of cellulose acetate, cellulose acetate propionate, and cellulose acetate butyrate ,
Alkyl represented by R—P (OR ¹ ) (OR ² ) ═O (R is an alkyl group containing 6 to 22 carbon atoms, and R ¹ and R ² are each a hydrogen atom or an alkyl group) A composition containing 0.1 to 60% by weight of titanium dioxide surface-treated with phosphonic acid or alkylphosphonic acid ester ,
A cellulose ester resin composition for a ball game board, wherein the Izod impact strength is 90% or more when the value of the cellulose ester resin alone is 100%.

2nd invention of this invention is a sheet-like molded article obtained using the resin composition as described in 1st invention .

A third invention of the present invention is a laminated sheet obtained by laminating the sheet-like molded product according to the second invention with at least one or more members from the group of paper and wood.
The fourth invention of the present invention is a ball game board obtained by using the laminated sheet described in the third invention.

The present invention is a composition comprising titanium dioxide surface-treated with a cellulose ester resin and a phosphorus compound, wherein the Izod impact strength is 90% or more when the value of the resin composition alone is 100%. Therefore, the original impact resistance of the cellulose ester resin is not impaired.

Since the present invention is the cellulose ester resin composition described above in which the phosphorus compound is an alkyl phosphonic acid or an alkyl phosphonic acid ester, the original impact resistance of the cellulose ester resin is not impaired.

In the present invention, since the cellulose ester resin is the cellulose ester resin composition as described above, wherein the cellulose ester resin is at least one selected from the group consisting of cellulose acetate, cellulose acetate propionate, and cellulose acetate butyrate. Does not impair sex.

The cellulose ester resin according to the above, wherein the cellulose ester resin composition includes 40 to 99.9% by weight of a cellulose ester resin and 0.1 to 60% of titanium dioxide surface-treated with a phosphorus compound. Since it is a composition, the original impact resistance of the cellulose ester resin is not impaired.

Since the present invention is a sheet-like molded product obtained using the above-described resin composition, the original impact resistance of the cellulose ester resin is not impaired.
Since the present invention is a laminated sheet obtained by laminating the above-mentioned sheet-like molded product with at least one of a group of paper and wood, a laminated sheet that does not impair the original impact resistance of the cellulose ester resin is provided. can get.

Since the present invention is a ball game board obtained by using the laminated sheet described above, a ball game board that does not impair the original impact resistance of the cellulose ester resin can be obtained.

With respect to the action effect that brings about these effects, there are the following two points due to the phosphorus compound. The first effect is an effect of suppressing deterioration of the cellulose ester resin during melt kneading by sulfuric acid, which is a catalyst residue in the cellulose ester resin according to the component of the present invention, by the phosphorus compound.

When melt-kneading cellulose ester resin, sulfuric acid, which is a catalyst residue during resin polymerization, reacts with cellulose ester resin and promotes deterioration due to molecular chain breakage, resulting in reduced impact resistance of the resulting molded product. End up. However, since the phosphorus compound deactivates sulfuric acid, which is a catalyst residue, it is assumed that molecular cleavage of the cellulose ester resin can be suppressed.

The second effect is that not only the cellulose ester resin system related to the constituent elements of the present invention, but also the knowledge of the molding process for all resins, especially thermoplastic resins, This is thought to be due to the reaction acceleration and deterioration of the cellulose ester resin caused by the active species.

Various reaction activations caused by this titanium dioxide have been reported, and those are also listed in the patent literature. However, until now, the details of the white-colored sheet of the present application have not been examined, and analysis in a strict sense has not been made. It was the actual situation.

The present application has further elucidated the solution to this problem, and has searched for a solution focusing on the types of titanium dioxide, particularly surface treatment. With regard to surface treatment, the purpose has been to disperse titanium dioxide in the resin, or the stability associated therewith, but in the present application, as described above, the reaction is promoted and deteriorated. Attention was paid to the processing of the present application.

There are various things related to the effect of phosphorus compounds, but it is presumed to be due to a kind of treatment effect that covers the reaction promotion and active species of titanium dioxide.

By surface-treating titanium dioxide with a phosphorus compound, the above two effects can be obtained at the same time, and the effect can be achieved with a smaller amount of addition than separately adding titanium dioxide surface-treated with a phosphorus compound and a phosphorus compound. Since it is obtained, efficiency is high.

<Cellulose ester resin>
Examples of the cellulose ester resin used in the present invention include organic acid esters such as cellulose acetate, cellulose propionate, and cellulose butyrate, inorganic acid esters such as cellulose nitrate, cellulose sulfate, cellulose acetate, and cellulose phosphate, and cellulose acetate propionate. In addition, mixed acid esters such as cellulose acetate butyrate and cellulose acetate phthalate can be mentioned. In particular, cellulose acetate, cellulose acetate propionate, and cellulose acetate butyrate are preferable because of excellent moldability.

These cellulose ester resins may contain a stabilizer and a plasticizer for improving moldability.

As the stabilizer, 2,6-di-t-butyl-p-cresol, 2,4,6-tri-tert-butylphenol, n-octadecyl-3- (4′-hydroxy-3 ′, 5′-di -Tertiary butylphenol) propionate, styrenated phenol, 4-hydroxy-methyl-2,6-di-tert-butylphenol, 2,5-di-tert-butyl-hydroquinone, cyclohexylphenol, butylhydroxyanisole, 2,2 '-Methylene-bis (4-methyl-6-tert-butylphenol), 2,2'-methylene-bis (4-ethyl-6-tert-butylphenol), 4,4'-isopropylidenebisphenol, 4,4' -Butylidene-bis (3-methyl-6-tert-butylphenol), 1,1-bis- (4-hydroxyphenyl) cyclohexa 4,4′-methylene-bis (2,6-di-tert-butylphenol), 2,6-bis (2′-hydroxy-3′-tert-butyl-5′-methylbenzyl) 4-methylphenol, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-tris-methyl-2,4,6-tris (3,5-di-tert 3-butyl-4-hydroxybenzyl) benzene, tetrakis [methylene-3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, tris (3,5-di-tert-butyl-4-hydroxy) Phenyl) isocyanurate, tris [β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanate, 4,4′-thiobis (3-methyl-6-tert-butyl) Nol), 2,2'-thiobis (4-methyl-6-t-butylphenol), 4,4'-thiobis (2-methyl-6-t-butylphenol), etc .; triphenyl phosphite , Tris (nonylphenyl) phosphite, triethyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, tris (tridecyl) phosphite, diphenyl mono (2-ethylhexyl) phosphite, diphenyl monodecyl phosphite, Diphenyl mono (tridecyl) phosphite, dilauryl hydrogen phosphite, diphenyl hydrogen phosphite, tetraphenyl dipropylene glycol diphosphite, tetraphenyl dipropylene glycol diphosphite, tetraphenyl te La (tridecyl) pentaerythritol tetraphosphite, tetra (tridecyl) -4,4′-isopropylidene diphenyl diphosphite, trilauryl trithiophosphite, bis (tridecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol Examples thereof include phosphite antioxidants such as diphosphite, tristearyl phosphite, distearyl pentaerythritol diphosphite, and tris (2,4-di-t-butylphenyl) phosphite. One or more of these stabilizers can be used.

As the plasticizer, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, dimethoxyethyl phthalate, ethyl phthalyl ethyl glycolate, butyl phthalate, which are general plasticizers used for plasticizing cellulose esters. Phthalic acid esters such as rubutyl glycolate, aromatic polycarboxylic acid esters such as tetraoctyl promitate, trioctyl trimellitate, dibutyl adipate, dioctyl adipate, dibutyl sebacate, dioctyl sebacate, diethyl azelate, dibutyl Lower fatty acids of polyhydric alcohols such as aliphatic polycarboxylic esters such as azelate and dioctyl azelate, glycerin, trimellirol propane, pentaerythritol and sorbitol Ester, triethyl phosphate, triphenyl phosphate, and phosphate esters such as tricresyl phosphate. These plasticizers can be used alone or in combination.

<Titanium dioxide>
The titanium dioxide used in the present invention may be produced by either a chlorine method or a sulfuric acid method. The crystal structure may be either anatase type or rutile type, but the rutile type is preferred from the viewpoint of weather resistance.

As the phosphorus compound used for the surface treatment of titanium dioxide in the present invention, alkylsulfonic acid or alkylsulfonic acid ester is preferable from the viewpoint of dispersibility in the cellulose ester resin, and more preferable is RP (OR ¹ ). (OR ² ) ═O (R is an alkyl group or cycloalkyl group containing 6 to 22 carbon atoms, and R 1 and R 2 are each a hydrogen, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group) And examples thereof include diethyl n-decane phosphonate, octyl phosphonic acid, and the like. These phosphorus compounds can be used alone or in combination.

The titanium dioxide in the present invention may be surface-treated with an inorganic compound in addition to the phosphorus compound. Examples of inorganic compounds include alumina, silica, titanium compounds, zirconium (Zr), zinc, magnesium and other metal compounds, and calcium compounds. These can be used alone or in combination.

In general, the surface treatment of titanium dioxide is performed first with an inorganic compound and then with an organic compound. Similarly, in the titanium dioxide in the present invention, the surface treatment with an inorganic compound is followed by the surface treatment with a phosphorus compound.

A conventionally known method can be used for the surface treatment with an inorganic compound of titanium dioxide. For example, a water-soluble aluminum salt as an inorganic surface treatment agent and other water-soluble metal salt as necessary are added to a titanium dioxide slurry, and then the pH in the slurry is adjusted to reduce the pH of the slurry with a hardly soluble oxide hydrate. The method of surface-treating a titanium pigment is mentioned.

A conventionally known method can be used for the surface treatment with the phosphorus compound of titanium dioxide. For example, when titanium dioxide is pulverized with a pulverizer, an alcohol solution of a phosphorus compound is added, and the surface treatment is performed by evaporating the alcohol while heating. Further, as a simple method, there is a method in which an alcohol solution of a phosphorus compound is dropped and mixed while stirring and mixing the titanium dioxide powder with a Henschel mixer or the like, and the alcohol is evaporated to perform surface treatment while heating.

The average particle diameter of titanium dioxide used in the present invention can be used as long as it is in a generally available range (0.1 to 0.4 μm), but it is 0.2 to 0.3 μm from the viewpoint of dispersibility and coloring power. Is preferred.

<Cellulose ester resin composition>
In the cellulose ester resin composition of the present invention, the cellulose ester resin is 40 to 99.9% by weight, and the proportion of titanium oxide 0.1 to 60% by weight is surface-treated with a phosphorus compound. From the viewpoint of If the amount of titanium oxide is lower than 0.1%, sufficient coloring power cannot be obtained.

<Other ingredients>
The cellulose ester resin composition in the present invention may contain additives such as pigments, antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, and inorganic fillers that are generally used in thermoplastic resins.

As pigments, titanium yellow, disazo yellow, isoindolinone yellow, polyazo yellow, polyazo red, quinacridone red, DPP red, perylene red, phthalocyanine green, phthalocyanine blue, dial, ultramarine, dioxazine violet, carbon black, iron black, etc. Is mentioned. These can be used alone or in combination.
As the antioxidant, one type or two or more types of antioxidants such as phenol type, phosphorus type, sulfur type and lactone type used for preventing thermal deterioration during resin processing can be used.

As the ultraviolet absorber and light stabilizer, benzophenone, hindered amine, benzotriazole, nickel quencher, cyanoacrylate compounds and the like are used. These can be used alone or in combination.

Examples of the antistatic agent include cationic, anionic and nonionic surfactants. It is also possible to use polymer-type permanent antistatic agents developed in recent years. These can be used alone or in combination.

Examples of the inorganic filler include talc, mica, calcium carbonate, barium sulfate, clay, silica, and the like, and the rigidity and heat distortion resistance of the molded product can be improved. These can be used alone or in combination.

<Sheet molded product>
The sheet molded product in the present invention can be obtained by a known method. As one of the methods, there is a method in which the cellulose ester resin composition is melt-kneaded with a single-screw or twin-screw kneader / extruder equipped with a T-shaped die and wound with a roll.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. In the examples and tables, “%” represents “% by weight”.
[Example 1]
A commercially available rutile-type titanium dioxide pigment was mixed with water and adjusted to an aqueous slurry having a weight of titanium dioxide pigment of 300 g / liter using a sand mill. While maintaining this slurry at 60%, sodium aluminate was added in an amount of 0.3% with respect to the weight of the titanium dioxide pigment in terms of Al ₂ O ₃ while stirring, and then neutralized to pH 5.0 with sulfuric acid. The surface of the titanium dioxide pigment was coated with aluminum hydrated oxide, filtered and washed with a filter press, and the resulting cake was dried at 120 ° C. for 10 hours to obtain a base titanium dioxide pigment (a).

Next, an aqueous solution obtained by diluting n-octylphosphonic acid twice with methanol is added when the base titanium dioxide pigment (a) is pulverized with a steam mill, and titanium dioxide is deposited on the surface of the titanium dioxide pigment (a). The titanium dioxide pigment (b) was obtained by coating so that the coating amount was 0.3% with respect to the pigment (a) weight.

Coating treatment Titanium dioxide pigment (b) 40%, cellulose acetate propionate resin (manufactured by Eastman, Tenite Propionate 307E40000-09) 60% melt-kneaded extrusion at a temperature of 200 ° C in a twin-screw kneading extruder A pellet-like colored resin composition (master batch) was obtained.

The obtained master batch and cellulose acetate propionate resin (manufactured by Eastman, Tenite Propionate 307E40000-09) are diluted and mixed at a rate of 10% of titanium dioxide, and an injection molding machine (Toshiba Machine Co., Ltd.) IS100-F) was injection molded at 180 ° C. to prepare an Izod impact test test piece described in ASTM D256. About the obtained test piece, the Izod impact strength was measured according to the Izod impact test method described in ASTM D256. In addition, the Izod impact strength was measured by the same method using a cellulose acetate propionate resin (manufactured by Eastman, Tenite Propionate 307E40000-09) alone.

Furthermore, the above master batch and cellulose acetate propionate resin (manufactured by Eastman, Tenite Propionate 307E40000-09) are diluted and mixed at a rate of 10% titanium dioxide, and an injection molding machine (Toshiba Machine Co., Ltd.) IS100-F) was injection molded at 180 ° C. to prepare test pieces for testing bending properties described in ASTM D790 and tensile properties described in ASTM D638, and each test was performed.

[Example 2-4]
Titanium dioxide, a masterbatch, and an Izod impact test test piece were prepared in the same manner as in Example 1 in accordance with the formulation in Table 1, and an Izod impact test was performed. In addition, the bending property and the tensile property were also tested in the same manner as in Example 1.

[Comparative Example 1-3]
Titanium dioxide, a masterbatch, and an Izod impact test test piece were prepared in the same manner as in Example 1 in accordance with the formulation in Table 1, and an Izod impact test was performed. In addition, the bending property and the tensile property were also tested in the same manner as in Example 1.

@
The titanium dioxide surface treatment agent of Examples and Comparative Examples and the concentration in the master batch, the Izod impact strength obtained by using these master batches, the bending properties and the tensile properties were also shown. In addition, Izod impact strength, bending properties and tensile properties of cellulose acetate propionate resin alone not containing titanium dioxide were also shown.

“Description of Table 1”
In Table 1, Izod impact strength was measured according to the method described in ASTM D256, bending properties were measured according to the method described in ASTM D790, and tensile properties were measured according to the method described in ASTM D638. In Example 1-4 according to the present application, the Izod impact strength value is equal to or higher (retention rate 100% or higher) compared to the value of the cellulose acetate propionate resin alone not containing titanium oxide. In Example 1-3, it was significantly reduced (retention rate 70% or less). Other mechanical properties such as bending properties and tensile properties were equivalent to those of the cellulose acetate propionate resin alone containing no titanium oxide. That is, the invention of the present application is useful not only in impact resistance but also in other mechanical properties in that the original characteristics of the cellulose resin are not impaired.

Claims (4)

40-99.9 wt% of a cellulose ester resin selected from at least one selected from the group consisting of cellulose acetate, cellulose acetate propionate, and cellulose acetate butyrate ;
Alkyl represented by R—P (OR ¹ ) (OR ² ) ═O (R is an alkyl group containing 6 to 22 carbon atoms, and R ¹ and R ² are each a hydrogen atom or an alkyl group) A composition containing 0.1 to 60% by weight of titanium dioxide surface-treated with phosphonic acid or alkylphosphonic acid ester ,
A cellulose ester resin composition for a ball game board, wherein the Izod impact strength is 90% or more when the value of the cellulose ester resin alone is 100%. A sheet-like molded article obtained by using the resin composition according to claim 1 . A laminated sheet obtained by bonding the sheet-like molded product according to claim 2 to at least one member from a group of paper and wood. A bullet ball game board obtained by using the laminated sheet according to claim 3 .