JP6282178B2 - Cellulose ester composition - Google Patents

Description

  The present invention relates to a cellulose ester composition.

Since cellulose esters such as cellulose acetate generally have poor thermoplasticity, they are usually used as a composition containing a plasticizer.
Patent Document 1 is an invention relating to a cellulose ester-based resin composition, and describes that a known plasticizer can be blended (paragraph number 0023).
Patent Document 2 is an invention relating to a resin composition composed of a cellulose ester having an average substitution degree of 2.7 or less, a plasticizer, and a filler.
However, there is a problem that the plasticizer in the resin bleeds out over time after the resin composition is produced or molded.

JP-A-10-306175 JP-A-2005-194302

  The present invention provides a cellulose ester composition having a molded article having excellent mechanical properties and suppressing bleed-out of a plasticizer.

As a means for solving the problems, the present invention
(A) For 100 parts by mass of cellulose ester,
(B) 2 to 100 parts by mass of a plasticizer,
(C) 0.5-10 parts by mass of a methyl methacrylate resin (excluding elastomer),
(D) 1-50 parts by mass of a thermoplastic elastomer containing a (meth) acrylic acid alkyl ester unit,
A cellulose ester composition is provided.

  According to the cellulose ester composition of the present invention, it is possible to obtain a molded article having excellent mechanical properties such as impact strength, tensile strength, bending strength and the like, and also suppressing bleed out of the plasticizer.

<(A) component>
The cellulose ester of the component (A) used in the composition of the present invention is a known one (for example, those described in Patent Document 1), cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate propio. Nate and cellulose acetate butyrate.
Other examples include polycaprolactone-grafted cellulose acetate, acetyl methyl cellulose, acetyl ethyl cellulose, acetyl propyl cellulose, acetyl hydroxyethyl cellulose, acetyl hydroxypropyl cellulose, and the like.

The cellulose ester as the component (A) is preferably cellulose acetate having an average substitution degree of 2.7 or less.
(A) As for the polymerization degree of the cellulose ester of a component, a viscosity average polymerization degree becomes like this. Preferably it is 100-1000, More preferably, it is 100-500.

<(B) component>
The plasticizer of the component (B) used in the composition of the present invention is a known one. (B) As a plasticizer of a component, 1 type chosen from the following plasticizer can be used, for example, It can also be used in combination of 2 or more types.
Aromatic carboxylic acid esters [dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, di-2-ethylhexyl phthalate, etc. C 1-6 Alkyl C 1-12 Alkyl Esters such as C 1-6 Alkyl C 1-12 Alkyl Esters, Phthalates, C 1-12 Alkyl Aryl-C 1-3 Alkyl Esters such as Butyl Benzyl Phthalate 6 alkylphthalyl C2-4 alkylene glycolate, trimethyl trimellitic acid, triethyl trimellitic acid, trioctyl trimellitic acid, trimellitic acid tri C1-12 alkyl ester, pyromellitic acid tetraoctyl such as trimellitic acid tri-2-ethylhexyl Such as Pyromellitic acid tetra C1-12 alkyl ester etc.],
Fatty acid esters [Adipic acid esters such as dibutyl adipate, dioctyl adipate, butoxyethoxyethyl benzyl adipate, dibutoxyethoxyethyl adipate, azelaic acid esters such as diethyl azelate, dibutyl azelate, dioctyl azelate, sebacic acid Dibutyl, sebacic acid esters such as dioctyl sebacate, butyl oleate, methylacetyl ricinoleate, etc.]
Among them, adipic acid ester is preferable.
Lower fatty acid esters of polyhydric alcohols (such as glycerin, trimethylolpropane, pentaerythritol, sorbitol) [such as diglycerin tetraacetate],
Glycol esters (such as dipropylene glycol dibenzoate),
Citrate esters such as acetyltributyl citrate,
Amides [N-butylbenzenesulfonamide, etc.]
Ester oligomers (such as caprolactone oligomers),
Other examples include phosphoric esters such as triphenyl phosphate which are also used as flame retardants.
The plasticizer as the component (B) is preferably selected from aromatic carboxylic acid esters and fatty acid esters.

  (B) Content of a component is 2-100 mass parts with respect to 100 mass parts of (A) component, Preferably it is 5-50 mass parts, More preferably, it is 10-40 mass parts.

<(C) component>
The component (C) used in the composition of the present invention is a methyl methacrylate resin, but does not include an elastomer.
The methyl methacrylate resin is a homopolymer polymethyl methacrylate (PMMA) or a methyl methacrylate copolymer using methyl methacrylate as a main component.
As a copolymer component of the methyl methacrylate copolymer,
Acrylic esters such as methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, phenyl acrylate, benzyl acrylate,
Examples thereof include methacrylic acid esters such as ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, and benzyl methacrylate.
Of these, methyl acrylate is preferred as the copolymer component of the methyl methacrylate copolymer.

  As a ratio (raw material basis) of methyl methacrylate in a methyl methacrylate copolymer, 80 mass% or more of methyl methacrylate is preferable, More preferably, it is 85 mass% or more, More preferably, it is 90 mass% or more.

The component (C) is preferably a methyl methacrylate resin having a weight average molecular weight of 30,000 to 100,000, more preferably a methyl methacrylate resin having a weight average molecular weight of 5,000 to 100,000.
The weight average molecular weight is a standard polystyrene equivalent value determined by GPC measurement using a tetrahydrofuran solvent.

  (C) Content of a component is 0.5-10 mass parts with respect to 100 mass parts of (A) component, Preferably it is 1-8 mass parts, More preferably, it is 1-6 mass parts.

<(D) component>
The component (D) used in the composition of the present invention is a thermoplastic elastomer containing a (meth) acrylic acid alkyl ester unit. In the present invention, “(meth) acrylic acid” is used to include both acrylic acid and methacrylic acid.
As the thermoplastic elastomer of component (D), a core-shell structure thermoplastic elastomer or a block copolymer structure thermoplastic elastomer can be used.
The core-shell structure thermoplastic elastomer is preferably a core-shell structure graft copolymer in which a monomer containing a (meth) acrylic acid alkyl ester constituting the shell is graft-polymerized with respect to the rubber-like polymer constituting the core.
As the thermoplastic elastomer having a block copolymer structure, a block composed of (meth) acrylic acid methyl ester units (Tg100 to 120 ° C) and a block composed of (meth) acrylic acid butylester units (Tg-40 to -50 ° C) ) Is preferred.

As a rubbery polymer constituting the core,
Polyalkyl acrylate rubbers such as butadiene rubber, isoprene rubber, polybutyl acrylate, poly (2-ethylhexyl acrylate), butyl acrylate / 2-ethylhexyl acrylate copolymer;
Silicone rubbers such as polyorganosiloxane rubber;
Butadiene-acrylic composite rubber, IPN composite rubber composed of polyorganosiloxane rubber and polyalkylacrylate rubber, styrene-butadiene rubber, ethylene-α olefin rubber (ethylene-propylene rubber, ethylene-butene rubber, ethylene-octene rubber, etc.), Examples thereof include ethylene-acrylic rubber and fluorine rubber. These can use 1 type (s) or 2 or more types. Among these, butadiene rubber and polyalkyl acrylate rubber (acrylic rubber) are preferable.
The (meth) acrylic acid alkyl ester is preferably methyl methacrylate or methyl acrylate.

As the component (D), a methyl methacrylate-butadiene copolymer (MB), a methyl methacrylate-acrylic rubber copolymer (MA), a methyl methacrylate-acrylic / butadiene rubber copolymer, and the like are preferable.
As the component (D), commercially available products can be used. For example, “Paraloid (registered trademark) EXL-2602” (core / shell type graft made of a butadiene-methyl methacrylate copolymer, manufactured by Rohm and Haas, Inc.) Copolymer), EXL-2603 (core / shell type graft copolymer comprising polybutadiene / alkyl acrylate / alkyl methacrylate copolymer), EXL-2633 (polybutadiene / alkyl acrylate / alkyl methacrylate copolymer) A core / shell type graft copolymer comprising a coalescence), “KURARITY (registered trademark)” (a block copolymer type) manufactured by Kuraray Co., Ltd., and the like.

  (D) Content of a component is 1-40 mass parts with respect to 100 mass parts of (A) component, Preferably it is 5-30 mass parts, More preferably, it is 5-25 mass parts.

The composition of this invention can contain a well-known thermoplastic resin according to a use.
Known thermoplastic resins include styrene resins such as ABS resin and AS resin, polycarbonate resins, polyolefin resins such as polyethylene and polypropylene, polyamide resins such as polyamide 6, polyamide 66, polyamide 610, and polyamide 612, and polyester. Resin, polyacetal resin, polyphenylene sulfide resin and the like.
40 mass% or less is preferable in the total amount with the cellulose ester of (A) component, and, as for the content rate of a well-known thermoplastic resin, 20 mass% or less is more preferable.

The composition of the present invention may further contain a filler.
Examples of the filler include fibrous fillers and non-fibrous fillers (powdered or plate-like fillers). For example, in paragraphs 0025 to 0032 of Patent Document 2 (Japanese Patent Laid-Open No. 2005-194302) Mention may be made of those described.
As for the content rate of a filler, 5-50 mass parts is preferable with respect to 100 mass parts of cellulose ester of (A) component, More preferably, it is 5-40 mass parts, More preferably, it is 5-30 mass parts.

The composition of the present invention can further contain a flame retardant.
As the flame retardant, a known one or a commercially available product can be used. In Japanese Patent Laid-Open No. 2003-261711, a naphthyl phosphate compound represented by the general formula (I), “PX-110”, an aromatic condensed phosphate ester, for example, Trade names “PX-200”, “CR-741”, “CR-733S”, “TCP”, etc., manufactured by Daihachi Chemical Industry Co., Ltd. can be used.
Other flame retardants include monomer types such as triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, trixylyl phosphate, dicresyl-2,6-dimethylphenyl phosphate, tris (2,6-dimethylphenyl) phosphate Organophosphorus flame retardants, resorcin bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), resorcin bis [(bis-2,6-dimethylphenyl) phosphate], hydroquinone bis [(bis-2,6-dimethylphenyl) ) Phosphate], 4,4′-biphenol bis [(bis-2,6-dimethylphenyl) phosphate] and other oligomeric organophosphorous flame retardants, magnesium hydroxide, aluminum hydroxide, melamine phosphate, Red phosphorus powders such as lamincyanurate, ammonium polyphosphate, melamine, thermosetting resin coated red phosphorus, olefin coated red phosphorus, titanium oxide coated red phosphorus and titanium aluminum condensate coated red phosphorus powder, silicone Silicone flame retardants such as resin, silicone grease, silicone rubber and silicone oil can be used.

  The composition of the present invention includes an epoxy compound described in paragraph Nos. 0035 to 0042 of Patent Document 2 (Japanese Patent Laid-Open No. 2005-194302), an organic acid, a thioether, a phosphite compound described in paragraph Nos. 0043 to 0052, and the like. The stabilizer may be contained.

  Depending on the application, the composition of the present invention may contain conventional additives such as other stabilizers (for example, antioxidants, ultraviolet absorbers, heat stabilizers, light stabilizers, etc.), colorants (dyes, Pigments, etc.), antistatic agents, flame retardant aids, lubricants, antiblocking agents, dispersants, fluidizing agents, anti-dripping agents, antibacterial agents and the like.

The composition of the present invention may be prepared by, for example, mixing each component in a dry or wet manner using a mixer such as a tumbler mixer, a Henschel mixer, a ribbon mixer, or a kneader.
Furthermore, after premixing with the mixer, a method of kneading with an extruder such as a single-screw or twin-screw extruder to prepare pellets, or a method of melting and kneading with a kneader such as a heating roll or a Banbury mixer is applied. can do.

  The composition of the present invention can be molded into various molded products by injection molding, extrusion molding, vacuum molding, profile molding, foam molding, injection press, press molding, blow molding, gas injection molding and the like.

  The composition of the present invention includes, for example, each part in the OA / home appliance field, the electrical / electronic field, the communication field, the sanitary field, the transportation vehicle field such as an automobile, the housing-related field such as furniture and building materials, the miscellaneous goods field, It can be used for a housing or the like.

  Examples and comparative examples

For other test items, each composition was used, and each evaluation test was performed by the method shown below. The evaluation results are shown in Table 1.
Using a Henschel mixer, each composition was stirred and mixed so that the frictional heat in the mixer would be 70 ° C or higher, then supplied to a twin-screw extruder (cylinder temperature: 200 ° C, die temperature: 220 ° C) and extruded. And pelletized.
The obtained pellets are supplied to an injection molding machine, and a test piece is injection molded under the conditions of a cylinder temperature of 200 ° C., a mold temperature of 50 ° C., and a molding cycle of 30 seconds (injection 15 seconds, cooling time 15 seconds), Used for each evaluation test.

<Use ingredients>
(A) Cellulose acetate, manufactured by Daicel Corporation, trade name “L50”, substitution degree 2.5, viscosity average polymerization degree 180
・ Product name “L20”, substitution degree 2.5, viscosity average polymerization degree 150, manufactured by Daicel Corporation
(B) Plasticizer / DAIFATTY 101: manufactured by Daihachi Chemical Industry Co., Ltd., adipic acid ester plasticizer (C) methyl methacrylate resin / 560F: manufactured by Asahi Kasei Chemical Co., Ltd., trade name “Delpet 560F”, methacrylic Methyl acrylate / methyl acrylate copolymer (containing 90% by mass or more of methyl methacrylate component), weight average molecular weight 81,000
LG2: manufactured by Sumitomo Chemical Co., Ltd., trade name “SUMIPEX LG2”, methyl methacrylate / methyl acrylate copolymer (containing 90% by mass or more of methyl methacrylate component), weight average molecular weight 76,000
(D) Thermoplastic Elastomer / EXL-2602: manufactured by Rohm & Haas Co., Ltd., “Paraloid (registered trademark) EXL-2602” (core / shell type graft copolymer made of butadiene-methyl methacrylate copolymer)
<Others>
・ T150: manufactured by Daicel Polymer Co., Ltd., trade name “Cebian T150”, acrylonitrile / methyl methacrylate / butadiene / styrene copolymer (MABS)

<Measurement test>
(MFR)
The measurement was performed at 220 ° C. and a load of 10 kg.

(Tensile strength / tensile nominal strain)
Based on ISO527, the tensile strength and the tensile nominal strain of the test piece were measured (tensile strength unit: MPa, tensile nominal strain unit:%).

(Bending strength / flexural modulus)
It was measured according to ISO178 (unit: MPa).

(Charpy impact strength)
Charpy impact strength (kJ / m ² ) was measured according to ISO 179 / 1eA (unit: KJ / m ² ).

(Plasticizer bleed out)
When the test sample (5 cm × 9 cm × 3 mm thick injection molded piece) was left in an atmosphere of 65 ° C. and 85% RH for 500 hours or 800 hours, the presence or absence of bleed-out was observed with the naked eye.

(Layer peeling)
In the test sample after the bending strength test, the sample that did not peel in layers was not present, and the sample that was peeled in layers was defined as having.

Claims (4)

(A) For 100 parts by mass of cellulose ester,
(B) 10-50 parts by mass of an adipate plasticizer,
(C) 1 to 6 parts by mass of methyl methacrylate / methyl acrylate copolymer (excluding elastomer)
(D) 5 to 25 parts by mass of a thermoplastic elastomer containing a (meth) acrylic acid alkyl ester unit,
A cellulose ester composition comprising:
(D) Cellulose ester, wherein the thermoplastic elastomer is a core-shell graft copolymer obtained by graft-polymerizing a monomer containing (meth) acrylic acid alkyl ester to a rubbery polymer selected from butadiene rubber and polyalkyl acrylate rubber Composition. (A) a cellulose ester, cellulose acetate, cellulose acetate propionate, those selected from cellulose acetate butyrate, claim 1 Symbol placement of a cellulose ester composition. (A) The cellulose ester composition of Claim 1 or 2 whose cellulose ester is a cellulose acetate of substitution degree 2.7 or less. Furthermore, the cellulose-ester composition of any one of Claims 1-3 containing a filler.