JPH05105812A - Resin composition for nail or screw - Google Patents

Abstract

PURPOSE:To provide a resin composition for nails or screws excellent in impact strength and moldability and very excellent in the response to nailing. CONSTITUTION:The title composition comprisies 50-100wt.% nylon 4, 6 (polytetramethyleneadipamide) (A), 0-50wt.% amorphous polyamide resin (B), 0-40wt.% olefin polymer (C) containing functional groups and 20-200 pts.wt., per 100 pts.wt. total of (A) to (C), inorganic filler (D).

Description

Detailed Description of the Invention

[0001]

The present invention relates to (A) polytetramethylene adipamide (hereinafter referred to as nylon 4, 6),
The present invention relates to a resin composition for nails or screws, which comprises an amorphous polyamide resin (B), a functional group-containing olefin polymer (C), and an inorganic filler (D).

[0002]

2. Description of the Related Art Nylon 4, 6 is a type of polyamide and has excellent properties as an engineering plastic,
In particular, it is known that the resin has excellent heat resistance. Generally, polyamide resins have excellent mechanical properties such as strength, impact resistance, and abrasion resistance, and have high heat resistance and chemical resistance, and also have good moldability. It is used in various applications such as general machine parts. Among them, nylons 4 and 6 have a high melting point, are excellent in heat resistance, have a short crystallization cycle because of a high crystallization rate, and have a low melt viscosity and thus have a good fluidity during molding. It has the feature that it exists. As described above, nylons 4 and 6 are excellent in chemical resistance of polyamide, and also excellent in heat resistance and moldability, and thus are expected to be applied as engineering plastics from various fields.

By the way, in general, nails and screws have conventionally been made of metal in many cases. However, metal nails and screws are unavoidable to rust, and when sawing wood with metal nails and screws remaining, the saw for sawing may spill or break, Not only must the saw blade for sawing be replaced, but if the broken blade hits the people around it, it could cause serious injury, which is dangerous.
Therefore, if the nails and screws, which were conventionally made of metal, are made of resin, there is no risk of rusting and it is safe during the lumbering process. Therefore, it has been considered to make the nails and screws resin. However,
When using resin for nails, screws, etc., in addition to being excellent in material strength, impact strength, and moldability, the feel of the worker when driving or screwing in, and the condition of the nail or screw It is necessary to have good (hereinafter referred to as "nail response"), and there was no resin composition that could satisfy all the above requirements.

[0004]

In view of the above circumstances, an object of the present invention is to provide a nail excellent in impact resistance (impact strength) and moldability when using resin nails and screws, and which is extremely excellent in nail response. And to provide a resin composition for screws.

[0005]

Means for Solving the Problems As a result of intensive studies conducted by the present inventors for such purposes, the constituent components (A) nylon 4,6 resin, (B) amorphous polyamide resin of the present invention,
It has been found that a resin composition for nails or screws comprising (C) a functional group-containing olefin polymer and (D) an inorganic filler solves the above problems and satisfies the object of the present invention.
The present invention has been reached.

That is, the present invention comprises (A) 50 to 100% by weight of polytetramethylene adipamide, (B) 0 to 50% by weight of an amorphous polyamide resin, and (C) 0 to 40% by weight of a functional group-containing olefin polymer. %, And (D) the inorganic filler 20 to 100 parts by weight of the total amount of (A) to (C).
The present invention relates to a resin composition for nails or screws, which comprises 200 parts by weight. Hereinafter, the present invention will be described according to constituent elements.

(A) Nylon 4,6 Nylon 4,6 used in the present invention mainly comprises polytetramethylene adipamide obtained from tetramethylene diamine and adipic acid and a polytetramethylene adipamide unit. And a copolyamide. Further, other polyamide may be contained as a mixed component within a range that does not impair the properties of nylons 4 and 6. The copolymerization component is not particularly limited, and a known amide-forming component can be used.

Typical examples of the copolymerization component include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminoundecanoic acid and para-aminomethylbenzoic acid, lactams such as ε-caprolactam and ω-lauryllactam. , Hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4-
/ 2,4,4-trimethylhexamethylenediamine, 5
-Methylnonamethylenediamine, metaxylylenediamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl)
Cyclohexane, 1-amino-3-aminomethyl-3,
Diamines such as 5,5-trimethylcyclohexane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, 2,2-bis (aminoprosyl) piperazine and aminoethylpiperazine Adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodiumsulfoisophthalic acid, hexahydroterephthalate Examples thereof include acids, dicarboxylic acids such as hexahydroisophthalic acid and diglycolic acid, and other polyamides used as a mixed component may include those composed of these components.

Nylon 4,6 used in the present invention
The manufacturing method of is arbitrary. For example, JP-A-56-149
430, JP-A-56-149431, JP-A-58-83029 and JP-A-61-4363.
No. 1, etc., that is, a prepolymer having a small amount of cyclic end groups is first produced under specific conditions, and then solid-state polymerized in a steam atmosphere to obtain high-viscosity nylon 4,
6 or a method of obtaining it by heating in a polar organic solvent such as 2-pyrrolidone or N-methylpyrrolidone.

The degree of polymerization of nylon 4,6 is not particularly limited, but it is 1 g / dl in 25 ° C. and 96% sulfuric acid.
Nylon 4,6 having a relative viscosity in the range of 2.0 to 6.0 is preferably used. The addition amount of nylon 4,6 in the present invention is 50 to 100% by weight, preferably 55 to 95% by weight, more preferably 60 to 9% by weight.
It is 0% by weight. 50% by weight of nylon 4,6 added
If less than, the impact strength is poor.

(B) Amorphous Polyamide Resin The amorphous polyamide resin used in the present invention is obtained from diamine, aromatic dicarboxylic acid and other aliphatic copolymerization component. Typical examples of the diamine constituting the amorphous polyamide resin include tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4. -Trimethylhexamethylenediamine, 5-methylnonamethylenediamine, 1,3-bis (aminomethyl) cyclohexane,
2, such as 1,4-bis (aminomethyl) cyclohexane
Mention may be made of linear and branched aliphatic diamines having -18 carbon atoms.

Further, as the diamine constituting the amorphous polyamide resin in the present invention, alicyclic diamine can be used. Typical examples of the alicyclic diamine are 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane and isophoronediamine. , Piperazine, 2,5-dimethylpiperazine, bis (4-aminocyclohexyl) methane, bis (4-aminocyclohexyl) propane,
4,4'-diamino-3,3'-dimethylcyclohexylmethane, 4,4'-diamino-3,3'-dimethylcyclohexylpropane, 4,4'-diamino-3,3 '
-Dimethyl-5,5'-dimethylcyclohexylmethane, 4,4'-diamino-3,3'-dimethyl-5,
5'-dimethylcyclohexylpropane, bis (4-amino-3-methyl-5-ethylcyclohexyl) methane, bis (4-amino-3-methyl-5-ethylcyclohexyl) propane, bis (4-amino-3,5 -Diethylcyclohexyl) methane, bis (4-amino-3,
5-diethylcyclohexyl) propane, bis (4-amino-3-methyl-5-isopropylcyclohexyl)
Methane, bis (4-amino-3-methyl-5-isopropylcyclohexyl) propane, bis (4-amino-)
3,5-diisopropylcyclohexyl) methane, bis (4-amino-3,5-diisopropylcyclohexyl) propane, bis (4-amino-3-ethylcyclohexyl) methane, bis (4-amino-3-ethylcyclohexyl) propane, Bis (4-amino-3-isopropylcyclohexyl) methane, bis (4-amino-3-)
Isopropylcyclohexyl) propane, α-α′-bis (4-aminocyclohexyl) -p-diisopropylbenzene, α-α′-bis (4-aminocyclohexyl) -m-diisopropylbenzene, α-α′-bis (4- Aminocyclohexyl) -1,4-cyclohexane, α-α'-bis (4-aminocyclohexyl)-
Those derived from aliphatic alkylenediamines such as 1,3-cyclohexane are mentioned.

Typical examples of the aromatic dicarboxylic acid constituting the amorphous polyamide resin include isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, and a mixture thereof, particularly isophthalic acid or isophthalic acid. And a mixture of terephthalic acid is preferably used.
Typical examples of other aliphatic copolymerization components constituting the amorphous polyamide resin include 6-aminocaproic acid and 11-aminocaproic acid.
Amino acids such as aminoundecanoic acid, ε-caprolactam, ω-lauryllactam and other lactams having 4 to 12 carbon atoms, aliphatic dicarboxylic acids such as adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, etc. Can be mentioned.

To obtain good physical properties, the relative viscosity of the amorphous polyamide resin (1% by weight of the amorphous polyamide resin)
(Measured at 20 ° C. using a meta-cresol solution)
It is desirable to be in the range of 5.0. In order to adjust the relative viscosity of the amorphous polyamide resin, it is possible to add a known monofunctional amine or carboxylic acid at the time of polymerization. The amorphous polyamide resin thus obtained has no melting point and is transparent.

When the amorphous polyamide resin is used in the resin composition of the present invention, a molded product having excellent moldability and appearance can be obtained. The addition amount of the amorphous polyamide resin in the present invention is 0 to 50% by weight, preferably 5 to 45% by weight, more preferably 10 to 35% by weight. Amount of amorphous polyamide resin added is 50% by weight
If it exceeds, the impact strength will be poor.

(C) Functional Group-Containing Olefin Polymer When the functional group-containing olefin polymer is used in the present invention, the compatibility between the constituent components (A) and (B) of the present invention becomes good. This functional group-containing olefin polymer is a binary or multi-component polymer mainly composed of an olefin unit and an unsaturated compound unit having at least one functional group selected from a carboxyl group, an acid anhydride group, an oxazoline group and an epoxy group. Is a copolymer of.

Typical examples of olefins in the above copolymer include ethylene, propylene, butene, pentene,
Hexene, heptene, methylbutene, methylpentene and the like can be mentioned, with ethylene and propylene being preferred.

Acrylic acid, methacrylic acid, maleic acid and the like are typical examples of the carboxyl group-containing unsaturated compound in the above copolymer, and anhydrous are typical examples of the acid anhydride group-containing unsaturated compound. There are maleic acid, itaconic anhydride, etc., representative examples of the oxazoline group-containing unsaturated compound include vinyl oxazoline, etc., and representative examples of the epoxy group-containing unsaturated compound include glycidyl methacrylate and allyl glycidyl ether. is there.

The types of functional groups preferably used in the present invention include acid anhydride groups and epoxy groups. Further, with respect to the above-mentioned copolymer, for example, by containing a vinyl compound in the main chain or by graft-polymerizing as a side chain, the heat resistance of the functional group-containing olefin polymer used in the present invention can be increased, and the composition It has the effect of further improving the compatibility with other components in the product, and is preferable for the purpose of the present invention.
The addition amount of the functional group-containing olefin polymer in the present invention is 0 to 40% by weight, preferably 2 to 35% by weight,
More preferably, it is 3 to 30% by weight. If the addition amount of the functional group-containing olefin polymer exceeds 40% by weight, the nail response is poor.

(D) Inorganic Filler The inorganic filler used in the present invention is various fillers having a fibrous shape, a powdery shape, a granular shape, a plate shape, a needle shape, a cloth shape, and a mat shape. Typical examples of such inorganic fillers include glass fiber, asbestos fiber, carbon fiber, graphite fiber, calcium carbonate, talc, catalbot, wollastonite, silica, alumina, silica-alumina, diatomaceous earth, clay and calcined clay. , Kaolin, mica (fine mica), granular glass, glass flakes, glass balloons (hollow glass), gypsum, red iron oxide, metal fibers, titanium dioxide, potassium titanate whiskers, magnesium oxide, calcium silicate, asbestos, sodium aluminate , Calcium aluminate, aluminum, aluminum oxide, aluminum hydroxide, copper, stainless steel, zinc oxide, metal whiskers and the like. For the purpose of the present invention, glass fiber, carbon fiber, kaolin, mica, and talc are preferable, and glass fiber, kaolin, mica, and talc are particularly preferable because of their economical efficiency. It may be surface-treated as long as it does not impair the moldability and physical properties of the present invention, and among them, those subjected to surface treatment represented by aminosilane treatment, acrylsilane treatment, vinyl treatment and the like are preferable.

The addition amount of the inorganic filler in the present invention is 20 to 200 parts by weight, preferably 30 to 100 parts by weight based on 100 parts by weight of the total amount of the constituent components (A) to (C) of the present invention.
180 parts by weight, more preferably 40 to 150 parts by weight. If the addition amount of the inorganic filler is less than 20 parts by weight, the nail response is poor, and if it exceeds 200 parts by weight, there is a problem in workability, particularly extrusion moldability and injection moldability.

Further, in the resin composition for nails or screws of the present invention, other polymers such as polyptadiene (PB), polyethylene (PE), ethylene-propylene copolymer may be used depending on the performance required from the application. (EP and EPDM), butadiene-styrene copolymer, styrene-ethylene-butadiene-styrene copolymer (SEB
S), allyl rubber (AR), fluororubber (FR), acrylonitrile-butadiene-styrene copolymer (AB
S), acrylonitrile-ethylene-styrene copolymer (AES), acrylonitrile-styrene copolymer (A
S), polystyrene (PS), polyethylene terephthalate (PET), polybutylene terephthalate (PB)
T), polyester mixture, polycarbonate (P
C), polysulfone, polyether sulfone (PE
S), polyimide (PI), PPS, polyetheretherketone (PEEK), vinylidene fluoride polymer (P
VDF), polyoxymethylene (POM), polytetrafluoroethylene (PTFE), polyphenylene ether (PPE), polyamides other than nylon 4,6,
Crosslinked particles and the like and modified products thereof can be appropriately blended.

In the resin composition for nails or screws of the present invention, other components such as pigments, dyes, colorants, organic reinforcing materials, heat-resistant agents, etc. can be used as long as the moldability and physical properties are not impaired.
Flame retardants, flame retardant aids, stabilizers represented by copper compounds and hindered phenol compounds, antioxidants, photoprotective agents,
Crosslinking agents typified by styrene maleic anhydride and epoxy compounds, weathering agents, light stabilizers, crystal nucleating agents, lubricants, release agents, plasticizers, antistatic agents and the like can be added and introduced. The resin composition for nails or screws of the present invention is a molding method which is used for ordinary thermoplastic resins such as injection molding, extrusion molding, blow molding, vacuum molding, compression molding, etc. Can be molded into various molded products.

The resin composition for nails or screws of the present invention comprises
Various nails, screws, screw lids, pins, sleeves, bolts and nuts, couplers, valves, nipples, sockets, elbows,
Parts such as hose ends, joints, cocks, plugs, connectors, adapters, unions, union cloths such as three-pronged parts, caps, taps, and other parts, and parts associated with these parts are molded and used. In addition, secondary processing such as painting, vapor deposition, and adhesion can be applied to such a molded part.

[0025]

The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The performance of the samples described in Examples and Comparative Examples was measured by the following method. 1) Impact strength: ASTM D256 (23 ° C, with notch) 2) Nail response: When a resin composition is molded into a nail and hammered into wood in a storage area, a worker feels when hammering the nail. The degree of sharpness of the nails and the hammered nails were evaluated. 3) Moldability: During the injection molding of the above test piece, the moldability and the appearance of the molded product were judged comprehensively and relatively, and "the moldability and the molding appearance were extremely good; ◎, good; ○, somewhat poor; △ , Poor; x ”.

The following materials were used in Examples and Comparative Examples. Constituent (A); Nylon 4, 6 as Dutch D
STANYL-KS300 manufactured by SM was used. As a comparative material, polyphenylene sulfide (PPS) resin “Torelina (containing 40% glass fiber)” manufactured by Toray Industries, Inc. was used.

Component (B): As the amorphous polyamide resin, the following amorphous polyamides (a) to (e) were used. The amorphous polyamide (a) is an amorphous polyamide composed of hexamethylenediamine, bis (4-amino-3-methylcyclohexyl) methane, terephthalic acid, isophthalic acid and caprolactam. The amorphous polyamide (b) is an amorphous polyamide composed of hexamethylenediamine, isophoronediamine, terephthalic acid, isophthalic acid and caprolactam. Amorphous polyamide (c) is "Trogamide T" manufactured by Dynamid Nobel.
(Trimethylhexamethylenediamine and terephthalic acid type amorphous polyamide). Amorphous polyamide (d)
Is an amorphous polyamide based on hexamethylenediamine and isophthalic acid (polyhexamethyleneisophthalamide). Amorphous polyamide (e) is hexamethylenediamine, bis (4-amino-3-methylcyclohexyl)
Methane, bis (4-amino-3-methyl-5-ethylcyclohexyl) methane, terephthalic acid, isophthalic acid,
It is an amorphous polyamide obtained from caprolactam.

Component (C); As the functional group-containing olefin polymer, an olefin polymer containing an acid anhydride group and an olefin polymer containing an epoxy group were used.
As the olefin polymer containing an acid anhydride group, a maleic anhydride-modified ethylene-propylene copolymer (modified EP) was used. As an olefin polymer containing an epoxy group, MODIPER A4 manufactured by NOF CORPORATION
101 was used. This is a graft copolymer having a main chain of ethylene-glycidyl methacrylate copolymer (85 wt% of ethylene component, 15 wt% of glycidyl methacrylate component) and a styrene polymer in the side chain (the weight ratio of the main chain to the side chain is 1 to 1).

Component (D): Glass fiber was used as the inorganic filler. As a glass fiber, the aspect ratio indicated by the ratio of the length in the longitudinal direction to the average diameter of the cross section is about 2
00, a chopped strand having an average diameter in the cross section of about 10 to 20 μm was used.

The resin compositions of Examples and Comparative Examples were pelletized with a twin-screw extruder (cylinder temperature 290 to 320 ° C.). A predetermined test piece was prepared from the obtained pellets by an injection molding machine (cylinder temperature 290 to 320 ° C.) and used for the test. As examples and comparative examples, the compositions and the evaluation results of the above items are shown in Tables 1 to 3 below.

[0031]

[Table 1]

[0032]

[Table 2]

[0033]

[Table 3]

Examples 1 to 8 Examples 1 to 8 are all resin compositions for nails or screws within the scope of the claims of the present invention. Example 1 is composed of components (A) and (D), and Example 2 is composed of components (A) and (B).
(D), Example 3 is a case where the constituent components (A), (C) and (D) are used, and Example 4 is a case where the constituent components (A), (B), (C) and (D) are used. As a resin composition for use, good evaluation results were obtained. In addition, Examples 4 to 8 are cases where the constituent component (B) is replaced with (a) to (e),
In all cases, good evaluation results were obtained as the resin composition for nails or screws. In Examples 9 to 11, the constituent components (A) to (D) were varied within the scope of the claims of the present invention, but good evaluation results were obtained as resin compositions for nails or screws. Further, it is shown that the effect of the constituent component (B) is to improve the moldability and the effect of the constituent component (C) is to improve the impact strength.

Comparative Examples 1 to 6 Comparative Examples 1 to 6 are resin compositions for nails or screws which are outside the scope of the claims of the present invention. Comparative Example 1 is a case where the constituent component (A) is less than the scope of claims of the present invention, and results are inferior in all of impact strength, nail response and moldability. Comparative Example 2 is a case where the constituent component (A) is less than the scope of the claims of the present invention and the constituent component (B) exceeds the scope of the claims of the invention, and all of the impact strength, the nail response and the moldability are obtained. The result was inferior to. Comparative Example 3 is a component (C)
Is beyond the scope of the claims of the present invention, and although the impact strength was relatively high, the result was poor nail response and moldability. Comparative Example 4 is a case where the constituent component (D) is less than the scope of claims of the present invention, and although the impact strength is relatively high, the nail response and the moldability are inferior. Comparative Example 5
In the case where the constituent component (D) exceeds the scope of the claims of the present invention, the test piece could not be molded because of problems in processability, particularly extrusion processability, and neither evaluation item could be measured. Comparative Example 6 is a case where PPS resin was used instead of nylon 4 and 6, and results were inferior in all of impact strength, nail response and moldability.

[0036]

INDUSTRIAL APPLICABILITY As specifically shown in the examples, the present invention provides (A) nylon 4,6 resin, (B) amorphous polyamide resin, (C) functional group-containing olefin polymer, and ( D) A resin composition for nails or screws, which is composed of an inorganic filler and has excellent impact resistance (impact strength) and moldability, and which is extremely excellent in response to nails.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shuji Tsuchikawa 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd.

Claims (1)

[Claims] 1. (A) Polytetramethylene adipamide 50
˜100% by weight, (B) amorphous polyamide resin 0 to 50
20 to 200 parts by weight of the (D) inorganic filler with respect to 100 parts by weight of the total amount of the (C) functional group-containing olefin polymer (0) to 40% by weight, and the above (A) to (C). Resin composition for nails or screws.