JPH04327909A - Thermoplastic resin chip and compound chip - Google Patents

Abstract

PURPOSE:To make a desired additive on the surface or retain uniformly in a recessed section by means of blended oil, manufacture good compound chips and use the same suitably in the fields of master patch or drive blend compound by manufacturing thermoplastic resin chips of specified shape. CONSTITUTION:Thermoplastic resin chips, for example, polyethylene, acryl resin, ABS resin, polypropylene, poylethylene, polyamide or the like having 1-5mm outer diameter d1, 1-10mm length L1 and 0.5-4.5mm tubular body or 0.5-9mm deep recessed section as the inner diameter d2 is used. As blended oil, for example, 0.1-10 pts.wt. of silicone oil or fluidized paraffin or the like and 0.001-2.00 pts.wt. of an oxidation inhibitor, a light stabilizer, an ultraviolet absorbing agent, a metal inactive agent and the like as other additives are blended with 100 pts.wt. of said thermoplastic resin chips.

Description

[Detailed description of the invention]

0001

[Field of Industrial Application] The present invention relates to a thermoplastic resin chip having a specified shape, and the present invention relates to a thermoplastic resin chip having a specified shape.
The purpose is to provide a compound chip in which fillers and the like are well mixed.

0002

2. Description of the Related Art Thermoplastic resins are generally subjected to extrusion molding, injection molding, etc. in the form of pellets, and are finished into desired objects and used effectively in a wide range of fields. In addition, such resin pellets and various additives, fillers, pigments, etc. are generally blended using a masterbatch method or a direct addition dry blend method, and then injection molding or extrusion is performed. Molding is taking place. Alternatively, injection molding or extrusion molding may be performed after pelletizing a uniformly dispersed mixture using an extruder.

0003

[Problems to be Solved by the Invention] However, when blending the above-mentioned resin pellets with various additives, fillers, pigments, etc., the masterbatch method causes poor dispersion and problems when a small amount of master pellets is added. If a large amount is added, a problem arises in that the dispersion becomes non-uniform. In other words, a problem in the production of masterbatches is that additives, fillers, etc. are pelletized using an extruder, so when a small amount is added, uniform dispersion is effective, but when a large amount is added, poor dispersion occurs. , resulting in poor pelletization.

[0004] In addition, in the dry blending method of direct addition, when a small amount is added, the additives, fillers, etc. adhere uniformly around the resin pellet, but when a large amount is added, the additives, fillers, etc. adhere to the periphery of the resin pellet. In addition, secondary agglomerates are formed, resulting in poor dispersion. Furthermore, since it adheres to the surroundings of the blending equipment, there is a problem of fluctuations in the amount added.

[0005]

[Means for Solving the Problems] The present inventors have conducted extensive research in order to solve the problems in blending the above-mentioned resin pellets with various additives, fillers, etc. As a result, the present invention was completed by improving the shape of the resin pellets.

That is, according to the present invention, the outer diameter is 1 to 5 mm, the length is 1 to 10 mm, and (a) the inner diameter is 0.5 to 4 mm.
A thermoplastic resin chip having a tubular body of 5 mm or (b) a concave portion of 0.5 to 9 mm in depth is provided.

According to the present invention, 0.1 to 10 parts by weight of blend oil and 0.001 to 2 parts by weight of other additives are added to 100 parts by weight of the above specified thermoplastic resin chips.
A compound chip containing 0.00 parts by weight is provided.

The shape of the tubular body or concave portion of the thermoplastic resin chip of the present invention is not particularly limited as long as it has a specified outer diameter, length, inner diameter, or depth. Figures 1 to 10 show the morphology of typical thermoplastic resin chips of the present invention.
For example: FIG. 1 shows a tip that is a tubular body (pipe-shaped) having a predetermined outer diameter d1, inner diameter d2, and length L, respectively. FIG. 2 shows a chip having an outer diameter d1, a length L, and a concave portion having an inner diameter d2 and lengths (depths) L1 and L2 on both sides. FIG. 3 shows a chip having an outer diameter d1, a length L, and a concave portion having an inner diameter d2 and a length (depth) L1 on one side. FIG. 4 shows a chip having an outer diameter d1, a length L, and a wedge-shaped (V-shaped) concave portion on the outer surface having a depth d3 and an opening width of generally 0.5 to 4.5 mm in the form of a horizontal groove. FIG. 5 shows two wedge-shaped (V-shaped) recesses in a vertical groove shape with an outer diameter d1, a length L, and an opening width (diameter) W on the outer surface, an inner diameter d2, and a depth d3. It's a chip. In addition, a concave portion with a diameter d2 and a depth d3 is partially formed on the outer surface with an outer diameter d1 and a length L.
It is also possible to provide more than one. Further, as the shape of these concave portions, a U-shape or the like is also preferable. Note that the outer and inner surfaces of the chip may have the same or different combinations of circles or polygons.

[0009] Such a thermoplastic chip of the present invention can be obtained using a conventionally known molding method. For example, a tubular body or a resin chip having a groove-like concave portion on the outer surface is extruded using a mold set to a predetermined inner diameter and outer diameter or depth, and then cut to a predetermined length. can be easily obtained. In addition, after the above tubular body is partially heated and welded at regular intervals to join the inner tube part,
A chip having concave portions on both sides or one side can be obtained by cutting one side or the center of the joint into a predetermined length. In addition, a chip having a predetermined concave portion on the outer surface can be obtained by extruding a tubular body having a predetermined outer diameter, and then immediately molding it in a softened state using a mold having a convex portion corresponding to the predetermined concave portion. be able to.

The thermoplastic resin used in the present invention is not particularly limited, and includes, for example, polystyrene, acrylic resin, A
S resin, ABS resin, polypropylene, polyethylene,
Polyamide, polyethylene terephthalate, polymethylpentene, polybutene, polycarbonate, polyacetal, etc., and copolymers thereof, such as ethylene/propylene copolymer, propylene/butene-1 copolymer, and further, for example, polypropylene and polyethylene, polypropylene and polybutene. -1, the above-mentioned mixture of polypropylene and polystyrene is used. In addition, with such thermoplastic resins, it is possible to mold the desired chip by pre-blending essential additives such as stabilizers with the resin, or basic additives within the range that can be molded into the chip. good.

[0011] The blended oil used in the present invention is as follows:
There are no particular restrictions as long as the various additives, fillers, etc. blended into the thermoplastic resin chips can be uniformly dispersed.
For example, silicone oils such as dimethylsiloxane and methylphenylsiloxane; liquid paraffins; phthalate esters such as dioctyl phthalate and diisodecyl phthalate; for example, di-2-ethylhexyl adipate,
Aliphatic dibasic acid esters such as diisodecyl adipate and di-2-ethylhexyl sebatate; trimellitic acid esters such as trioctyl trimellitate and triisodecyl trimellitate; such as acetyltributyl citrate and acetyl tributyl citrate; Oxyacid esters such as -2-ethylhexyl; for example, epoxyhexahydrophthalate esters such as -2-ethylhexyl epoxyhexahydrophthalate and diisodecyl epoxyhexahydrophthalate.

Examples of additives and fillers to be incorporated into the compound chip of the present invention include antioxidants, antistatic agents, lubricants, dispersants, light stabilizers, ultraviolet absorbers, nucleating agents, clarifying agents, and inorganic Additives and fillers such as fillers, pigments, plasticizers, flame retardants, organic peroxides, and metal deactivators are used as necessary.

Regarding the above-mentioned main additives, specifically 1.
) Antioxidants include hindered phenols, such as octadecyl-3-(3,5-di-t-butyl-4-
hydroxyphenyl) propionate, pentaerythrityl-tetrakis [3-(3,5-di-t-butyl-4
-hydroxyphenyl)propionate], triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 3,
9-bis[2-{3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1
,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, etc.; phosphites, such as tris(2,4-di-t-butylphenyl)phosphite, distearylpenta Erythritol diphosphite, bis-(2,4-di-t-butylphenyl)pentaerythritol, diphosphite, tetrakis(2,4-di-t-butylphenyl)-4,4'-
Biphenylene phosphite, etc.; thioesters, such as dilaurylthiodipropionate, dimyristylthiodipropionate, distearylthiodipropionate, pentaerythritol tetrakis (β-laurylthiopropionate), etc.; amines, such as octylation diphenylamine, etc.; bisphenols, such as 2-t-butyl-6-(3'-t-butyl-5'-methyl-2'-
hydroxybenzyl)-4-methylphenylacrylate, 2,2'-ethylidenebis(4,6-di-t-butylphenol), etc.; vitamin E type, such as dl-α-tocopherol.

2) As the ultraviolet absorber, benzophenone type, such as 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone sulfonic acid, etc.; benzotriazole type , for example 2
-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole, etc.; salicylates, e.g. -t-butylphenyl salicylate, 2,4-di-t-butylphenyl-3',5'-di-t-butyl-4-hydroxybenzoate, n-hexadecyl-3,5-di-t-butyl-
4-hydroxybenzoate, etc.; substituted acrylonitrile-based ethyl-2-cyano-3,3'-diphenylacrylate, etc.

3) As the light stabilizer, hindered amine type, for example, bis(2,2,6,6-tetramethyl-4-
piperidyl) sebacate, dimethyl succinate 1-(2
-hydroxyethyl)-4-hydroxy-2,2,6,
6-tetramethylpiperidine polycondensate, poly[{6-(
1,1,3,3-tetramethylbutyl)amino-1,3
,5-triazine-2,4-diyl}{(2,2,6,
6-tetramethyl-4-piperidyl)imino}hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl)imino} and the like. Nickel complex systems, e.g. [2,2
'-Thiobis(4-t-octylphenolate)]n・
Butylamine nickel II, nickel complex
3,5-di-t-butyl-4-hydroxybenzyl phosphate monoethylate and the like.

4) Examples of metal deactivators include oxalic acid derivatives such as oxalyl bis(benzylidene hydrazide); salicylic acid derivatives such as 3-(N-salicyloyl)amino-1,2,4-triazole, etc. ; hydrazide derivative systems, e.g. N,N'-bis[3-(3',
5'-di-t-butyl-4'-hydroxyphenyl)propionyl]hydrazine, bis(2-phenoxypropionylhydrazide) phthalate, and the like.

5) As the lubricant, monoglyceride type,
For example, glycerol stearate, etc.; higher alcohols of fatty acids, such as stearyl alcohol; fatty acid monoamides, such as oleic acid amide, erucic acid amide,
Stearic acid amide, etc.; Bisamide type, such as ethylene bis stearic acid amide, hexamethylene bis stearic acid amide, ethylene bis oleic acid amide, etc. Fatty acids, such as stearic acid, behenic acid, etc.; metal salts of fatty acids, such as calcium stearate, aluminum stearate, zinc stearate, etc.

6) As antistatic agents, cationic ones such as quaternary ammonium salts, nonionic ones such as polyhydric alcohol esters of fatty acids, polyoxyethylene alkylamines, etc.; anionic ones such as alkyl phosphate salts, alkyl sulfones, etc. acid salts etc.

7) Nucleating agents include metal salts of aromatic carboxylic acids, such as aluminum pt-butylbenzoate, sodium benzoate, and sodium bis(4-t-butylphenyl) phosphate.

8) As a clarifying agent, benzylidene sorbitol type, for example, 1,3,2,4-dibenzylidene sorbitol, 1,3,2,4-di(methylbenzylidene) sorbitol, 1,3,2,4 -di(ethylbenzylidene)sorbitol, etc.

9) Examples of inorganic fillers include calcium carbonate, silica, magnesium sulfate, clay, and potassium titanate.

10) As the flame retardant, halogen type, such as 2,2-bis-[4-(2,3-dibromopropoxy)-3,5-dibromophenyl]propane, decabromodiphenyl oxide, etc.; phosphorus halogen type , such as ethylene bistris (2-cyanoethyl) phosphorium bromide; phosphorus-based materials such as ammonium polyphosphate, etc.
Inorganic systems, such as antimony trioxide, aluminum hydroxide,
Akarin et al.

11) Examples of pigments include zinc oxide, titanium oxide, iron oxide, ultramarine blue, carbon black, aniline black, chrome yellow, titanium yellow, quinacridone red, anthraquinone red, benzidine yellow, pigment scarlet, phthalocyanine green, and phthalocyanine blue.

12) Organic peroxides include diacyl peroxides such as benzoyl peroxide, lauroyl peroxide, decanoyl peroxide, etc.; alkyl peroxides such as dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,
5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, etc.; peracid esters such as t-butyl peracetate, t-butyl perpavirate, t-butyl perlaurate, perbenzoic acid t-butyl etc.

13) Dispersants include WAX, such as calcium montanate, ester adducts of calcium montanate, polyethylene wax, polypropylene wax, and the like.

[0026] The blending ratio in the compound chip of the present invention may be appropriately selected depending on the application, but generally 0.1 to 10 parts by weight of blend oil and 0.001 parts by weight of the resin compounding agent are added to 100 parts by weight of the thermoplastic resin chip. ~200
The ratio of parts by weight is preferable because the effects of the present invention are extremely clearly exhibited. In particular, 0.01 to 50 parts by weight of antioxidants, antistatic agents, lubricants, dispersants, light stabilizers, ultraviolet absorbers, nucleating agents, clarifying agents, metal deactivators, etc.
Pigments, colorants, organic peroxides, and the like are preferably 0.001 to 10 parts by weight, and inorganic fillers, flame retardants, and the like are preferably 1.0 to 200 parts by weight.

[0027] The resin compound chips of the present invention can be obtained by a known method of mixing resin chips, blended oil, and desired ingredients using, for example, a tumbler or a Henschel mixer. That is, the compounding agent is attached to the surface of the resin chip using blended oil as a medium, and if the desired amount of compounding is large, the mixing operation is performed until the compounding agent is deposited in the tubular part or recess (hole) of the resin chip. That's fine.

[0028]

[Operations and Effects] As understood from the above, the resin compound chip of the present invention uses a resin chip having a tubular or concave shape and a blended oil to cause the desired compounding agent to adhere to the surface and deposit on the tubular or concave portion. According to
Approximately the same amount can be held per resin chip. Therefore, the resin compound chip of the present invention is
Suitable for use in the field of masterbatches or dry blend compounds, and is also suitable for blending large quantities or substances with large differences in specific gravity, which are difficult to achieve with conventional methods due to poor dispersion or segregation phenomena. used for.

As a result, according to the present invention, even when a large amount of additives are used, not only is good pelletization possible due to uniformly dispersed resin compound chips, but also
Since it can be used as it is as a masterbatch, conventional kneading is not required (rationalization), and furthermore, it can be directly used for molding as it is. Furthermore, in the present invention,
Manufacture a predetermined chip with only basic stabilizers mixed in,
By preparing a compound chip by blending the chip with other additives according to the order, the chip can be shipped as a desired grade. That is, the present invention is extremely useful industrially, such as reducing off-grades due to grade changes, streamlining stable operation, reducing inventory, and being able to quickly respond to small-lot production of a wide variety of products.

[0030]

[Examples] The present invention will be specifically explained below based on Examples, but the present invention is not particularly limited to the following Examples. The measurement methods, additives, and polymers used in the following Examples and Comparative Examples are shown below.

1) Ash content measurement 5 g of the injection molded product cut into approximately 5 mm square pieces was weighed into a crucible. After gradually heating until almost all ash is formed, the mixture is allowed to cool and then ignited at 500°C. After cooling, the weight was measured to determine the ash content. Dispersibility was evaluated at n=3.

2) Fluorescent X-ray Analysis Using the injection molded product, S was detected by fluorescent X-ray analysis to determine the amount of additive components. Dispersibility was evaluated at n=3.

3) Additives and polymer A1: Dimethylsiloxane: SH200 Toray Co., Ltd.
Dow Corning Silicone A2: Methylphenylsiloxane
:SH710 Toray Dow Corning Silicon B
: Liquid paraffin : Moresco White P70 Matsumura Oil Research Institute C1 : Dioctyl phthalate : Sansocizer DOP Shin Nippon Chemical C2 : Diisodecyl phthalate : Sansocizer DIDP
New Japan Chemical D1: Di-2-ethylhexyl adipate
: Sansocizer DOA New Japan Chemical D2: Di-2-ethylhexyl sebacate
: Sansocizer DOS New Japan Chemical E : Trioctyl trimellitate
: Sansocizer TOTM New Japan Chemical F
: Acetyltributyl citrate
: Citroflex A-4 Pfizer G
:Epoxyhexahydrophthalate di-2-ethylhexyl
: Sansocizer E-PS New Japan Chemical H1
: Talc : Crown Talc P-3 Matsumura Sangyo H2 : Calcium carbonate
:Whiten P-30 Toyo Fine Chemical H3:Titanium oxide:DA
IREN WHITE W-120

Dainippon Ink Chemical Industry I: Pentaerythritol tetrakis (β-
lauryl thiopropionate)
:Sumilizer
TPD Sumitomo Chemical J1: Polypropylene (homotype MFR=9g/10min.):ME
140 Tokuyama Soda J2: Polypropylene (homotype MFR=23g/10min.): MJ160 Tokuyama Soda J3: Polypropylene (block copolymer type MFR=7g/10min.)

:MS640 Tokuyama Soda J4: Polypropylene (block copolymer type MFR=23g/10min.)

:MS670 Tokuyama Soda J5: Polypropylene (random copolymer type)
MFR=17g/10min. )

:ME451 Tokuyama Soda K1: Polyethylene (high density type MFR=7g/1
0 min. )
: Sumikasen Hard 2623
Sumitomo Chemical K2: Polyethylene (low density type)
MFR=7g/10min. )
: Sumikasen L705 Sumitomo Chemical L1: Polybutene-1 (MFR=4g/10min.)

: Polybutene M2481 Mitsui Petrochemical N
: Polypropylene powder (block copolymer type MFR=7g/10min.) Tris(2,4-di-t-butylphenyl)phosphite: Irgafos168 (Ciba Geigy)
0.05 parts by weight, pentaerythrityl-tetrakis
[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]: Irg
anox1010 (Ciba Geigy) 0.05 parts by weight,
Stear calcium phosphate (NOF) 0.
05 parts by weight P: Polystyrene
:Estyrene G20 Nippon Steel Chemical

Examples 1 to 28 Raw resin was processed using a 30 mmφ extruder (resin temperature 210°C
, crosshead die), outer diameter 3 mm x inner diameter 1.5 mm
After molding the pipe, it was cut into pieces of about 5 mm. obtained,
The compounds shown in Table 1 were blended with 100 parts by weight of pipe-shaped resin chips and thoroughly mixed using a Henschel mixer. This obtained mixture was put into a 150 ton injection molding machine (
A molded product of 50 mmφ x 1 mmt was produced at a resin temperature of 230°C. Using this molded article, the above-mentioned ash content measurement and fluorescent X-ray analysis were performed to evaluate the dispersibility. Table 1 summarizes the measurement results of ash content measurement and fluorescent X-ray analysis.
It was shown to.

[0035]

[Table 1]

Comparative Examples 1 to 15 Comparative Examples 1 to 15 were carried out in the same manner as in the Examples except that no blended oil was used. Table 2 shows the measurement results of ash content measurement and fluorescent X-ray analysis.

[0037]

[Table 2]

Comparative Examples 16 to 36 The compounds shown in Table 3 were blended with 100 parts by weight of resin pellets, and thoroughly mixed using a Henschel mixer. This obtained mixture was applied to a 150 ton injection molding machine (resin temperature
230° C.), a molded product of 50 mmφ×1 mmt was created. Using this molded product, the above-mentioned ash content measurement and fluorescence
Line analysis was measured and dispersion was evaluated. The measurement results of ash content measurement and fluorescent X-ray analysis are collectively shown in Table 3.

[0039]

[Table 3]

Comparative Example (Part 3) 37-40 The compounds shown in Table 4 were blended with 100 parts by weight of resin powder and mixed thoroughly using a Henschel mixer. Pellets were made from the obtained mixture using a 50 mmφ extruder (resin temperature: 210° C.). Next, 150 to
n injection molding machine (resin temperature 230℃), 50mmφ
A molded product of x1 mmt was created. Using this molded article, the above-mentioned ash content measurement and fluorescent X-ray analysis were performed to evaluate the dispersibility. The measurement results of ash content measurement and fluorescent X-ray analysis are collectively shown in Table 4.

[0041]

[Table 4]

Comparative Example (No. 4) 41-51 The compounds shown in Table 5 were blended with 100 parts by weight of the resin pellets and thoroughly mixed in a Henschel mixer. A masterbatch was prepared from the obtained mixture using a 50 mmφ extruder (resin temperature: 210° C.). Next, 100 parts by weight of the resin pellets were thoroughly mixed with the obtained masterbatch in the formulation shown in Table 6 using a Henschel mixer. This obtained mixture was molded into a 150 ton injection molding machine (resin temperature: 230°C).
), a molded product of 50 mmφ×1 mmt was created. Ash content measurement and fluorescence X-ray analysis were performed using this molded article to evaluate dispersibility.
The measurement results of the line analysis are collectively shown in Table 6. Also, Table 5
shows the pelletizing formability during masterbatch preparation.

[0043]

[Table 5]

[0044]

[Table 6]

Examples 29-38 and Comparative Examples 52-59
After extruding and molding the raw resin into pipes of various sizes having the outer diameter (d1) and inner diameter (d2) shown in Table 7 using a 3 mmφ extruder (resin temperature 210°C, crosshead die), ), and immediately after extruding a specified pipe, thermal fusion is performed at regular intervals, and the unfused portion is cut to form a specified length (L
) and a predetermined length (L1, L2) on both sides.

To 100 parts by weight of each of the chips obtained above, 2 parts by weight of liquid paraffin as a blend oil and 11 parts of polymerized talc as a filler were thoroughly mixed using a Henschel mixer. 150 tons of this mixture
50mmφ×1 with injection molding machine (resin temperature 230℃)
A molded product of mmt was created. The above-mentioned ash content was measured using this molded article, and the results are shown in Table 7.

[0047]

[Table 7]

[Brief explanation of drawings]

FIG. 1 is a schematic diagram showing a tubular tip.

FIG. 2 is a schematic diagram showing a chip having tubular recesses on both sides.

FIG. 3 is a schematic diagram showing a chip having a tubular recess on one side.

FIG. 4 is a schematic diagram showing a chip having one V-shaped recess on the surface.

FIG. 5 is a schematic diagram showing a chip having two V-shaped recesses on its surface.

[Explanation of symbols]

d1 Chip outer diameter d2 Inner diameter of tip d3 Depth of recess L Chip length L1 Length (depth) of recess L2 Length (depth) of recess

Claims (2)

[Claims] [Claim 1] Outer diameter 1 to 5 mm and length 1 to 10 m
m, and (a) a tubular body with an inner diameter of 0.5 to 4.5 mm, or (b) a thermoplastic resin chip having a concave portion with a depth of 0.5 to 9 mm. 2. A compound chip obtained by blending 0.1 to 10 parts by weight of blend oil and 0.001 to 200 parts by weight of other additives to 100 parts by weight of the thermoplastic resin chip according to claim 1. .