JP2000264975A - Master batch for adding to cellulose fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a master batch suitable for adding a cellulose fiber to a polyolefin by containing each specific ratio of the cellulose fiber, an oil and fat component having an iodine value in a specific range, a silane-coupling agent, a radicalgenerating agent, an elastomer and a polyolefin. SOLUTION: This master batch contains (A) 100 pts.wt. cellulose fiber, (B) 0.1-5 pts.wt. oil and fat component having >=50 iodine value, (C) 0.5-5 pts.wt. silane-coupling agent, (D) 4×10-5-1.5×103 mole radical-generating agent based on 100 pts.wt. component A, (E) 0-15 pts.wt. elastomer and (F) 5-28 pts.wt. polyethylene. The master batch is obtained by kneading a substance containing the components A to C to obtain a kneaded material, and then kneading the kneaded material with a substance containing the components D to F. The obtained master batch has preferably <=30% weight of its portion passing through 50-mesh screen and <=30% weight of its portion not passing through 10-mesh.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a masterbatch for adding cellulose fibers for a cellulose fiber-containing polyolefin and a method for producing the same. More specifically, the present invention relates to a masterbatch for adding cellulose fibers to a polyolefin such as an olefin resin or an elastomer, in which cellulose fibers are preferably added, and a method for producing the same.

[0002]

2. Description of the Related Art As polyolefins containing cellulose fibers, JP-A-57-185351 and JP-A-3-725.
No. 43 and the like are disclosed.

[0003]

In a conventional molded article comprising cellulose fiber and polyolefin, when kneading the cellulose fiber and the polyolefin, the cellulose fiber having a low bulk density is scattered or the dispersibility of the cellulose fiber and the polyolefin is reduced. , The resulting molded product had poor dispersibility, poor molded appearance, and poor physical stability. Therefore, the cellulose fiber and the polyolefin are uniformly dispersed, and a molded product composed of the cellulose fiber and the polyolefin can be easily produced, and the composition composed of the cellulose fiber and the polyolefin having stable physical properties and good appearance can be easily produced. A way was desired.

[0004]

According to the present invention, when kneading a cellulose fiber and a polyolefin, the cellulose fiber having a low bulk density is not scattered, and the dispersibility of the polyolefin such as an olefin resin or elastomer and the cellulose fiber is excellent. A masterbatch for adding cellulose fibers which can be added to a polyolefin and a method for producing the same have been found.

The present invention relates to a masterbatch for adding cellulose fibers for a cellulose fiber-containing polyolefin, wherein (1) 100 parts by weight of cellulose fibers, and (2) 0.1 to 5 parts by weight of an oil component having an iodine value of 50 or more. (3) 0.5 to 5 parts by weight of a silane coupling agent, and (4) a radical generator in an amount of 4 × 10 ⁻⁵ to 100 parts by weight of cellulose fiber.
The present invention relates to a masterbatch for adding cellulose fibers, comprising 1.5 × 10 ⁻³ mol, (5) 0 to 15 parts by weight of an elastomer, and (6) 5 to 28 parts by weight of polyethylene.

[0006] Preferably, the present invention relates to a masterbatch for adding cellulose fibers, which is produced by the following steps. (1) Step of kneading a cellulose fiber, an oil component having an iodine value of 50 or more, and a substance containing a silane coupling agent to produce a kneaded product A (2) Including a kneaded product A, an elastomer, polyethylene and a radical generator Of kneading materials and manufacturing master batch for adding cellulose fiber

[0007] More preferably, the present invention relates to a masterbatch for adding cellulose fibers, wherein the weight not passing through 50 mesh is 30% or less and the weight not passing through 10 mesh is 30% or less.

[0008]

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a masterbatch for adding cellulose fibers for a cellulose fiber-containing polyolefin, wherein (1) 100 parts by weight of cellulose fibers, (2)
An oil component having an iodine value of 50 or more, preferably 55 or more, more preferably 60 or more, and particularly preferably 70 or more.
5 to 5 parts by weight, preferably 0.5 to 4 parts by weight, more preferably 0.5 to 3 parts by weight, particularly preferably 0.5 to 2 parts by weight.
Parts by weight, (3) 0.5 to 5 parts by weight of a silane coupling agent, preferably 0.5 to 4 parts by weight, more preferably 0.5 to 3 parts by weight, particularly preferably 0.5 to 2 parts by weight,
(4) The radical generator is 4 × 10 ^{−5 to} 1.5 × 10 ⁻³ mol, preferably 4 × 10 ⁻⁵ mol per 100 parts by weight of the cellulose fiber.
× 10 ^-5 to 1 × 10 ^-3 mol, more preferably 5 × 10
^{-5 to} 5 × 10 ^-4 mol, particularly preferably 5 × 10 ^-5 to 2 ×
^10-4 mol, (5) 0 to 15 parts by weight of elastomer, preferably 0.01 to 15 parts by weight, more preferably 0.0 to 15 parts by weight.
5 to 15 parts by weight, particularly preferably 0.1 to 15 parts by weight, and (6) 5 to 28 parts by weight of polyethylene, preferably 5 to 25 parts by weight, more preferably 5 to 23 parts by weight, particularly preferably 5 to 23 parts by weight. The present invention relates to a masterbatch for adding cellulose fibers, comprising 20 parts by weight.

(2) The fat component is preferable in the above-mentioned range of the element value and in the above-mentioned range of the addition because of excellent dispersibility of the cellulose fiber.

(3) The silane coupling agent is preferable in the above-mentioned range of the addition amount because the dispersibility of the cellulose fiber is excellent.

(4) The radical generator is preferably used in the above-mentioned range because it does not generate a gel and has excellent dispersibility of cellulose fibers.

(6) Polyethylene is preferable in the above-mentioned range because of its excellent dispersibility of cellulose fibers.

[0013] In the masterbatch for adding cellulose fibers for the cellulose fiber-containing polyolefin of the present invention, when the masterbatch for adding cellulose fibers is added to an olefin resin, the compounding amounts of (5) elastomer and (6) polyethylene are (5) ) 0-10 parts by weight of elastomer, 0.1-10 parts by weight, especially 0.5-5 parts by weight, and (6) 5-25 parts by weight of polyethylene, further 5-2
3 parts by weight, especially 7 to 23 parts by weight, is preferable because of excellent dispersibility of the cellulose fiber and the polyolefin and stability of physical properties of the obtained molded product.

When the masterbatch for adding cellulose fibers for the cellulose fiber-containing polyolefin of the present invention is added to the elastomer, the compounding amounts of (5) elastomer and (6) polyethylene are (5) 1 to 15 parts by weight of an elastomer, further 1 to 10 parts by weight, especially 3 to 8 parts by weight, and (6) 5 to 20 parts by weight of polyethylene, further 5 to 15 parts by weight, especially 5 to 10 parts by weight of cellulose fiber It is preferable because the dispersibility with the elastomer and the stability of physical properties of the obtained molded product are excellent.

The polyethylene (6) used in the masterbatch for adding cellulose fibers of the present invention has a density of 0.
940 to 0.970, melt flow rate (MI) 0.
The high-density polyethylene of 1 to 15 or the ethylene-α-olefin copolymer or a mixture thereof is preferable because the dispersibility of the cellulose fiber and the polyolefin is excellent and the production of the master batch for adding the cellulose fiber is easy. [Melt flow rate (MI): JIS K721
0 and 190 ° C. using a melt indexer.
Weight of resin extruded in a strand shape in 10 minutes under a load of 2.16 kg]

The cellulose fiber-added masterbatch of the present invention can be used as pellets or powders formed using an extruder or the like.

The masterbatch for adding cellulose fibers of the present invention has a weight of 30% or less, more preferably 20% or less, particularly 15% or less, which passes through 50 mesh, and 30% or less, further 25%, which does not pass 10 mesh. The content is preferably 20% or less, in particular, since there is no scattering of powder, the handling is easy, and the dispersibility with polyolefin is excellent.

The masterbatch for adding cellulose fibers of the present invention is preferably produced by the following steps, since a cellulose fiber is excellent in dispersibility, physical properties are stable and a homogeneous product can be obtained. (1) Step of kneading a cellulose fiber, an oil component having an iodine value of 50 or more, and a substance containing a silane coupling agent to produce a kneaded product A (2) Including a kneaded product A, an elastomer, polyethylene and a radical generator Of kneading materials and manufacturing master batch for adding cellulose fiber

The master batch for adding cellulose fibers of the present invention is further produced by the following steps,
30% or less, more preferably 20% or less, particularly 15% or less, and the weight not passing through 10 mesh, which is excellent in handleability without powder scattering and excellent in dispersibility with polyolefin, is 30% or less. 30% or less, more preferably 25% or less, especially 20% or less is preferable because it can be obtained without molding a powdery master batch for adding cellulose fibers. (1) Step of kneading a cellulose fiber, an oil component having an iodine value of 50 or more, and a substance containing a silane coupling agent to produce a kneaded product A (2) Including a kneaded product A, an elastomer, polyethylene and a radical generator Of kneading materials and manufacturing master batch for adding cellulose fiber

In the masterbatch for adding cellulose fibers, (1) the step of kneading a cellulose fiber, a fat or oil component having an iodine value of 50 or more, and a silane coupling agent to produce a kneaded material A comprises: The fiber, the oil or fat component having an iodine value of 50 or more, and a substance containing a silane coupling agent are mixed at a lower limit of 100 ° C, further 110 ° C, particularly 115 ° C to an upper limit of 200 ° C, further 150 ° C.
It is preferable to knead in a temperature range of 130 ° C, particularly 130 ° C.

In the step of kneading (2) the kneaded product A of the master batch for adding cellulose fiber, a material containing an elastomer, polyethylene and a radical generator to produce a master batch for adding cellulose fiber, (2) kneaded product A,
Elastomer, a product containing polyethylene and a radical generator, 100 ° C as a lower limit, further 110 ° C, particularly from 120 ° C to an upper limit of 200 ° C, further 170 ° C,
In particular, it is preferable to knead in a temperature range of 140 ° C.

Cellulose fibers are fibers such as natural cellulose fibers containing cellulose as a main component and artificial cellulose fibers. Examples of natural cellulose fibers include seed hair fibers, gin skin fibers, leaf fibers, and wood fibers, and examples of artificial cellulose fibers include regenerated cellulose fibers and semi-synthetic fibers. In particular, the cellulose fiber is preferably a natural cellulose fiber.

The cellulose fiber is preferably made of paper, waste paper, wood flour, hemp, cotton, wood, etc., which are mainly composed of natural cellulose fiber, such as KC floc and paper powder. The size of the cellulose fiber is not particularly limited, but in consideration of processability, handleability, compatibility with polyolefins such as polyethylene, and the strength of a molded product, the diameter is 5 to 80 μm, and the fiber length is 0. 05-
Those having a 5.0 mm average fiber length of 0.1 to 3 mm are preferred.

When the water content of the cellulose fiber is increased, water is foamed during molding with the polyolefin composition to roughen the surface of the molded article or accelerate the deterioration of the resin during molding. Therefore, the upper limit is 10% by weight or less. preferable.

Oil components having an iodine value of 50 or more include linseed oil (iodine value 170-204) and cottonseed oil (iodine value 99-204).
113), natural animal and vegetable fats and oils such as olive oil (iodine value 79-90), corn oil (iodine value 109-133), rapeseed oil (iodine value 97-107), lard oil (iodine value 53-77), and linoleic acid And fatty acids such as unsaturated fatty acids having an iodine value of 50 or more such as oleic acid. These can be used alone or as a mixture of two or more. Further, the oil component having an iodine value of 50 or more is a fatty acid such as an unsaturated fatty acid having 6 or more carbon atoms, further 8 or more carbon atoms, particularly 11 or more carbon atoms and an iodine value of 50 or more, or an animal or vegetable natural oil or fat having an iodine value of 50 or more. Are preferred. Vegetable natural fats and oils can be preferably used because they are inexpensive and can be easily obtained, and can reduce product costs. Particularly, vegetable natural fats and oils such as olive oil and rapeseed oil having an iodine value of 50 to 150, preferably 50 to 140, and more preferably 60 to 140 are preferable because the obtained polyolefin composition and this molded article do not have odor. The iodine value of natural fats and oils is
Encyclopedia of Chemistry (11th edition of a compact edition published on February 5, 1971,
Publisher: Kyoritsu Shuppan).

As the silane coupling agent, a silane compound represented by the general formula (1), more preferably, the general formula (2) can be used.

[0027]

Embedded image (Wherein, R ₁ represents a γ-methacryloxypropyl group, a vinyl group, an alkenyl group, a γ-acryloyloxypropyl group, a 6-acryloyloxyhexyltriethoxy group, an ethynyl group, a 2-propynyl group, an amino group, R ₂ , R ₃ , and R ₄ represent a mercapto group or an epoxy group;
A methoxy group, an ethoxy group, a 2-methoxyethoxy group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an octyl group, a cyclohexyl group, an acetoxy group, a benzyl group or a phenyl group.

[0028]

Embedded image (Wherein, R ₁ is a γ-methacryloxypropyl group, R ₂ , R ₃ , and R ₄ are methoxy, ethoxy, methyl, ethyl, propyl, butyl, pentyl,
Octyl, cyclohexyl, benzyl or phenyl)

Examples of the silane coupling agent include γ-methacryloxypropyltrimethoxysilane,
Vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, 3
-Aminopropyltriethoxysilane, 3-glucidoxypropyltrimethoxysilane, 3-glucidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, Examples thereof include 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane.

As the radical generator, a dicumyl-based compound, an azo-type or other decomposition-type radical generator, a peroxide-type radical generator, or the like can be used. As the radical generator, for example, dicumyl peroxide, benzoyl peroxide, tert-butyl benzoate, di-te
rt-butyl peroxide, 2,5-dimethyl-2,
5-di (tert-butylperoxy) hexane, te
rt-butyl hydroperoxide, α, α′-di (t
tert-butylperoxy) diisopropylbenzene,
Examples thereof include persulfate compounds such as isopropyl percarbonate and ammonium persulfate, and tetravalent tin compounds such as dibutyltin oxide. Of these, one or a combination of two or more thereof can be used.

The cellulose fiber-containing masterbatch of the present invention can be added to a polyolefin to produce a cellulose fiber-containing polyolefin. As the polyolefin, a polyolefin such as an olefin resin and an elastomer can be used. As the polyolefin, a resin produced from a single-site catalyst such as a metallocene catalyst can be used.

As the olefin resin, except for the following elastomers, low-density polyethylene (LDPE), high-density polyethylene (HDPE), ethylene-α-olefin copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl chloride copolymer Polyethylene, polypropylene (PP), polypropylene such as polypropylene-α-olefin copolymer, poly-1-butene, poly-4-
Polypentenes such as methyl-1-pentene and mixtures thereof can be used.

As the elastomer, natural rubber (NR),
Synthetic isoprene rubber (IR), styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (N
Rubber components such as (BR), ethylene-propylene-diene terpolymer (EPDM), chloroprene (CR), halobutyl rubber (XIIR), butyl rubber (IIR), and thermoplastic elastomer (TPO), and mixtures thereof are preferred.

The masterbatch for the addition of cellulose fiber of the present invention may be, depending on the intended use, a lubricant such as a higher aliphatic amide, metal soap, glycerin ester, an anti-calendering tacking agent such as natural silica, synthetic silica, talc, diatomaceous earth, or phenol. System, phosphorus system, antioxidant such as BHT, UV absorber such as benzophenone, benzotriazole, HALS, aluminum hydroxide, magnesium hydroxide,
Phosphorus-based, halogen-based flame retardants, silica excluding cellulose fiber, calcium carbonate, mica, carbon black,
Inorganic and organic fillers such as titanium oxide, pigments such as azo-based, phthalocyanine-based, quinacridone-based, iron oxide, and ultramarine blue, antistatic agents, surfactants, and antibacterial agents can be added.

The polymer batch other than the above-mentioned polyolefin can be added to the cellulose fiber-added masterbatch of the present invention, depending on the application.

The production of the masterbatch for the addition of cellulose fibers of the present invention is generally carried out by various well-known mixers, for example, a structure in which a stirring blade such as a plate type, a propeller type or a Faudler type is rotated in a mixing tank. A ball mill, a crusher, a shaker, or the like having a structure in which a stirring ball flows in a mixer or a mixing tank can be used. As various mixers, general various powder mixers can be used,
In particular, it can be manufactured using a high-efficiency mixer such as a Henschel mixer, a Schuler, a ribbon blender, a Brabender, a Banbury mixer, or an extruder such as a single screw or twin screw.

[0037]

The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited to these examples.

The characteristic values were measured as follows. [Evaluation method]-Evaluation of dispersibility of cellulose fiber The sample for evaluation was prepared using an injection molding machine (Fanuc C-30A type (manufactured by FANUC)) under the molding conditions of a barrel temperature of 180 ° C and a mold temperature of 60 ° C. 0.7 × 127 × 3.2
mm. The appearance of the molded product was visually observed to evaluate the dispersibility of the cellulose fibers. Good: Almost no white part due to poor dispersion of cellulose fibers was observed on the surface of the sample. Poor: Many white portions due to poor dispersion of cellulose fibers are observed on the surface of the sample.

Evaluation method of xylene solubility 200 g of xylene at 100 ° C. was added to 1 g of the master batch, heated at 100 ° C. for 60 minutes, and filtered through a 50-mesh wire net. The presence or absence of a gel material remaining on the wire net was visually observed. Yes: gel-like substance was found, no: gel-like substance was not found

Evaluation method of particle size distribution A sieve including a 50-mesh and a 10-mesh standard sieve is placed on a 10-mesh standard sieve above the 50-mesh standard sieve and attached to an electromagnetic sieve shaker.
After charging 10 g of the master batch into 10 mesh, the mixture was shaken for 30 minutes. The weight remaining on the 10 mesh and the weight passing through the 50 mesh were measured.

Example 1 A master batch for adding cellulose fiber was produced in the following two steps. Step 1 Cellulose fiber (KC Floc: W-10) shown in Table 1
0 (manufactured by Nippon Paper Industries, average fiber length 0.15 mm), 100 parts by weight of linseed oil, 1 part by weight of γ-methacryloxypropyltrimethoxysilane (KBM503: manufactured by Shin-Etsu Chemical Co., Ltd.) at 120 ° C. using a Henschel mixer. Rotation speed 13
The mixture was mixed at 50 rpm for 10 minutes to produce a kneaded material A.

Step 2 102 parts by weight of the kneaded material A and HDPE-a shown in Table 1
(M3800: manufactured by Keiyo Polymer) 10 parts by weight, EPDM
2 parts by weight of EP22 (manufactured by JSR) and 0.04 parts by weight of benzoyl peroxide (BPO) were put into a Banbury mixer heated to 130 ° C., kneaded at 155 rpm for 10 minutes, and a master batch A for adding cellulose fibers was prepared. Was manufactured. Benzoyl peroxide (BPO)
0.04 parts by weight is 1.65 × 10 ^-4 mol / 100 parts by weight of cellulose fiber.

The particle size distribution and xylene solubility of the master batch A for adding cellulose fibers were evaluated, and the results are shown in Table 2.

Evaluation of dispersibility of cellulose fiber The cellulose fiber-added master batch A and the polyolefin shown in Table 2 were kneaded with a twin-screw extruder so that the cellulose fiber became 50 parts by weight, and pelletized cellulose fiber was obtained. Was obtained. A sample for evaluating the dispersibility of cellulose fibers was formed from the obtained polyolefin composition containing cellulose fibers, and the results of evaluation of the dispersibility of cellulose fibers of the formed samples are shown in Table 2.

[0045]

[Table 1]

Examples 2 to 6 and Comparative Examples 1 to 5 The same procedures as in Example 1 were carried out except that the amounts of cellulose fibers, oils and fats, silane coupling agents, olefin resins, elastomers and peroxides shown in Table 1 were used. A masterbatch or a kneaded product for adding cellulose fibers was produced in two steps in the same manner as in 1.

Evaluation The particle size distribution and xylene solubility of the masterbatch or kneaded material for adding cellulose fibers were evaluated, and the results were shown in Table 2.
It was shown to. -Evaluation of dispersibility of cellulose fiber The master batch or kneaded product for adding cellulose fiber and the polyolefin shown in Table 2 were kneaded with a twin-screw extruder so that the cellulose fiber became 50 parts by weight, and pelletized cellulose fiber was obtained. A polyolefin composition was obtained.
A sample for evaluating the dispersibility of cellulose fibers was formed from the obtained polyolefin composition containing cellulose fibers, and the results of evaluation of the dispersibility of cellulose fibers of the formed samples are shown in Table 2.

Example 7, Comparative Example 6 The procedure of Example 1 was repeated except that the amounts of cellulose fiber, oil and fat, silane coupling agent, olefin resin, elastomer and peroxide shown in Table 1 were used. In two steps, a masterbatch or kneaded material for adding cellulose fibers was produced.

Evaluation The particle size distribution and xylene solubility of the obtained master batch or kneaded product for adding cellulose fibers were evaluated, and the results are shown in Table 2. The masterbatch or kneaded product for addition of cellulose fibers and the polyolefin shown in Table 2 were kneaded with a twin-screw extruder so that the cellulose fibers became 30 parts by weight to obtain a polyolefin composition containing cellulose fibers in pellet form. . A sample for evaluating the dispersibility of cellulose fibers was formed from the obtained polyolefin composition containing cellulose fibers, and the results of evaluation of the dispersibility of cellulose fibers of the formed samples are shown in Table 2.

[0050]

[Table 2]

[0051]

According to the masterbatch for adding cellulose fibers of the present invention, a composition in which the cellulose fibers and the polyolefin are uniformly dispersed, the physical properties are stable, and the molding appearance is good can be easily and easily produced.

By manufacturing the master batch for adding cellulose fibers of the present invention in two steps, a master batch having good handleability and good dispersibility of cellulose fibers can be easily manufactured.

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Claims (3)

[Claims] 1. A masterbatch for adding cellulose fibers for a cellulose fiber-containing polyolefin, comprising: (1) 100 parts by weight of cellulose fibers; (2) 0.1 to 5 parts by weight of a fat or oil component having an iodine value of 50 or more; 3) 0.5 to 5 parts by weight of the silane coupling agent, and (4) 4 × 10 ^{−5 to} 1.5 × 10 ⁵ based on 100 parts by weight of the radical generator.
^-3 moles, (5) 0 to 15 parts by weight of an elastomer, and
(6) A masterbatch for adding cellulose fibers, comprising 5-28 parts by weight of polyethylene. 2. The masterbatch for adding cellulose fibers according to claim 1, which is produced by the following steps. (1) Step of kneading a cellulose fiber, an oil component having an iodine value of 50 or more, and a substance containing a silane coupling agent to produce a kneaded product A (2) Including a kneaded product A, an elastomer, polyethylene and a radical generator Of kneading materials and manufacturing master batch for adding cellulose fiber 3. The masterbatch for adding cellulose fibers according to claim 1, wherein the weight not passing through 50 mesh is 30% or less and the weight not passing through 10 mesh is 30% or less.