JPH048762A - Flexibilizer for polyamide resin and polyamide resin composition for molding - Google Patents

Abstract

PURPOSE:To provide a flexibilizer for polyamide resin, containing OH group or COOH group, composed of a glycidylated product of a hydrogenated conjugated diene polymer and capable of providing a polyamide resin molding composition giving a molded article having excellent flexibility, etc. CONSTITUTION:The objective flexibilizer for polyamide resin is composed of a glycidylated product containing OH group or COOH group, having an average molecular weight of 200-20,000 (preferably 500-10,000) and an epoxy equivalent of 200-20,000g/eq (preferably 100-15,000g/eq) and produced by reacting a hydrogenated conjugated diene polymer (preferably hydrogenated polybutadiene glycol or hydrogenated polyisoprene glycol) with epichlorohydrin at 30-70 deg.C in the presence of sodium hydroxide. The molding composition can be produced by compounding a polyamide resin with 1-500wt.% (preferably 2-400wt.%) (based on the polyamide resin) of the above flexibilizer and mixing and reacting the components under melting.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a flexibility imparting agent for polyamide resins and a polyamide resin composition for molding. More specifically, the present invention relates to a flexibility imparting agent for polyamide resin molded articles and a flexible polyamide resin composition for molding.

[Prior Art] Conventionally, as flexibility imparting agents for polyamide resin molded products,
There are polymers that have rubber elasticity. As a polymer having rubber elasticity, a method is known in which, for example, liquid polybutadiene having hydroxyl or carboxyl groups or hydrogenated liquid polyisoprene having similar groups is added (for example, JP-A-64-1999-1). 51449).

[Problems to be solved by the invention] However, because these terminal groups are hydroxyl or carboxyl groups, they have poor reactivity with polyamide resins, and the incorporation of rubber-elastic polymers into resins is insufficient. be. Therefore, there were problems in that the flexibility of the polyamide resin molded product was insufficient and the impact resistance was poor. Moreover, those having unsaturated bonds such as liquid polybutadiene have the problem of being easily deteriorated by oxidation and having poor heat aging resistance.

Means for Solving Problem E] The present inventors have made extensive studies to solve these problems, and as a result, have arrived at the present invention. That is, the present invention provides a flexibility-imparting agent for polyamide resin (B) comprising a glycidylated product (A) of a hydrogenated conjugated diene polymer containing a hydroxyl group or a carboxyl group; Glycidylated products of hydrogenated conjugated diene polymers containing hydroxyl or carboxyl groups (
This is a molding polyamide resin composition characterized by containing a reaction product with A).

In the present invention, examples of the hydrogenated conjugated diene polymer containing a hydroxyl group or a carboxyl group include hydrogenated polybutadiene glycol, hydrogenated polyisoprene glycol, hydrogenated poly1,3-pentadiene glycol, Hydrogenated conjugates containing hydroxyl groups such as hydrogenated polycyclopentadiene glycol, hydrogenated poly(butadiene-isoprene) glycol, hydrogenated poly(butadiene-styrene) glycol, hydrogenated poly(isoprene-styrene) glycol, etc. Diene polymers; and hydrogenated conjugated diene polymers containing carboxyl groups such as hydrogenated polybutane dicarboxylic acid and hydrogenated polyisoprene dicarboxylic acid.

Among these, preferred are those containing a hydroxyl group, and particularly preferred are hydrogenated polybutadiene glycol and hydrogenated polyisoprene glycol.

In the present invention, the glycidylated product (A) is a hydroxyl group-containing, hydrogenated conjugated diene polymer obtained by glycidyl etherification of the hydroxyl group, or a carboxyl group-containing, hydrogenated conjugated diene polymer. The carboxyl group of is converted into a glycidyl ester.

The method for producing the glycidylated product (A) is not particularly limited, but includes, for example, the conventionally known one-stage method and two-stage method. In the one-step method, a hydrogenated conjugated diene polymer containing a hydroxyl group or a carboxyl group is reacted with epichlorohydrin at 30 to 70°C in the presence of caustic soda to produce the glycidylated product (A). I can do it.

In the two-step method, the glycidylated product ( A) can be produced. Among these, the one-stage method is preferable because it allows the glycidylated product (A) with a lower total chlorine content to be obtained. The glycidylated product (A)
The average molecular weight of is usually 200 to 20,000, preferably
500-1oooo. If it is less than 200, the flexibility effect of the molded product obtained from the composition of the present invention is insufficient,
When it exceeds 20,000, the melt fluidity of the polyamide resin composition deteriorates, and the moldability deteriorates. The epoxy equivalent of the glycidylated product (A) is 200 to 20000 g/e
Q, preferably 100 to 15000 g/eQ.

In the present invention, the polyamide resin (B) includes, for example, polycapramide (nylon-6), polyhexamethylene adipamide (nylon-6°6), polyhexamethylene civamide (nylon 6.10), polyhexamethylene adipamide (nylon-6.10), Examples include methylenedodecamide (nylon-6, 12L) polyundecaneamide (nylon-11), polydodecanamide (nylon-12), and copolymerized or condensed polyamides containing these as main components.

In the polyamide resin composition of the present invention, the amount of the glycidylated product (A) used is usually 1 to 500%, preferably 2 to 400%, based on the weight of the polyamide resin (B).
%. If it is less than 1%, the effect of improving the impact resistance of the molded product is low. If it exceeds 500%, the melt flowability and moldability of the polyamide resin composition will decrease.

Furthermore, in the polyamide resin composition of the present invention, in order to increase the crosslinking density of the resin, a crosslinking agent for polyamide can be used in combination when producing the composition, if necessary. This crosslinking agent is generally used for crosslinking the polyamide resin (B) and/or for crosslinking the polyamide resin (B) and the glycidylated product (A).
) is added for the purpose of increasing the crosslinking density of the molded product through crosslinking, lowering the water absorption rate, and further improving the heat aging resistance. Examples of the crosslinking agent include silane coupling agents, alcohol-modified melamine resins, and tetraalkyl titanates. As the silane coupling agent, for example, general formula X-8iY3 (X
is an organic functional group such as an epoxy group, an amino group, a mercapto group, or a vinyl group, and Y is an alkoxyl group. Examples of the alcohol-modified melamine resin include butoxymethylated melamine resin, methoxymethylated melamine resin, and hydroxymethylated melamine resin. Examples of the tetraalkyl titanate include tetrabutyl titanate. Also,
A mixture of two or more of these crosslinking agents may also be used. Among these, silane coupling agents having epoxy groups are preferred because they can sufficiently increase the crosslinking density of the molded product. Specific examples of the silane coupling agent having an epoxy group include γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and the like.

In addition to the crosslinking agent, the composition of the present invention may contain various additives as necessary. Examples of this additive include curing accelerators (phosphorous compounds such as triphenylphosphine and triphenyl phosphite; 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, Imidazoles such as 2-ethyl-4-methylimidazole;
2-(dimethylaminomethyl)phenol, 2. Tertiary amines such as 4゜6,-tris(dimethylaminomethyl)phenol, benzyldimethylamine, α-methylbenzylmethylamine; 1,8-diazabicyclo(5,
4,0) organic acid salts such as undecene-7); fillers (silica, barium sulfate, etc.); pigments (carbon, titanium oxide, red red iron, etc.); thixotropic agents (colloidal silica, etc.), and the like.

The method for producing the composition of the present invention is not particularly limited, but for example,
A mixture of the polyamide resin CB), the glycidylated products (A) and M, and optionally the above-mentioned crosslinking agents, curing accelerators, fillers, pigments, thixotropic agents, and other additives, is usually heated at a temperature higher than the melting point of the polyamide resin ( Preferably from 200℃ to 30℃
0°C), and. Examples of the apparatus used for this melt mixing include a Brabender kneader-Banbury mixer-plasto mill, a roll kneader, an extruder, and the like. The polyamide resin composition of the present invention can be molded into the desired shape by various molding methods, such as extrusion molding, injection molding, compression molding, etc., depending on the purpose, to obtain a flexible polyamide resin molded product. .

[Example] Hereinafter, the present invention will be further explained with reference to Examples, but the present invention is not limited thereto. In the following, parts and % indicate parts by weight and % by weight, respectively.

Example 1 100 parts of nylon-6 and 100 parts of glycidyl ether of hydrogenated polybutadiene glycol (MW = 2500, ff-poxy equivalent = 1600 g/eq) were melt-kneaded using an extrusion molding machine to obtain the inventive product. A polyamide resin composition was prepared. The obtained polyamide resin composition was injection molded to create a sorted molded sample having a thickness of 2 mm. The physical properties of this product are shown in Tables 1 and 2.

Example 2 100 parts of nylon-6 and 100 parts of glycidyl ether of hydrogenated polyisoprene glycol (MW = 2500, z poxy equivalent = 1400 g/eq) were melt-kneaded using an extruder to produce the polyamide resin of the present invention. It was made into a composition. The obtained polyamide resin was injection molded to create a sheet-like molded product sample with a thickness of 2 mm. The physical properties of this product are shown in Tables 1 and 2.

Example 3 Nylon-e: 100 parts, glycidyl ether of hydrogenated polybutadiene glycol of Example 1: 100 parts, and γ-
10 parts of glycidoxypropyltrimethoxysilane were melt-kneaded using an extruder to obtain a polyamide resin composition of the present invention. The obtained polyamide resin composition was injection molded to create a sheet-like molded product sample with a thickness of 2 mm.

The physical properties of this product are shown in Tables 1 and 2.

Comparative Example 1 Using 100 parts of nylon-6 as a polyamide resin, liquid polybutadiene having a hydroxy group (hydroxyl group equivalent = 1.88 m
A sheet-like molded product sample with a thickness of 2 mm was prepared in the same manner as in Example 1 except that 100 parts of eQ/g) was used. The physical properties of this product are shown in Tables 1 and 2.

Comparative Example 2 Using 100 parts of nylon-6 as the polyamide resin, hydrogenated liquid polyisoprene having hydroxyl groups (hydroxyl equivalent = 0.9) was used instead of the glycidyl ether of Example 1.
A sheet-like molded product sample with a thickness of 2 mm was prepared in the same manner as in Example 1 except that 100 parts of 3meQ/g) were used. The physical properties of this product are shown in Tables 1 and 2.

Table 1 Initial physical properties note) l 'x2 JIS K Ei911 With notch; Compliant with.

Compliant with ASTM D25 [i.

Table 2 Physical property change rate after heat aging test 3 (%) Conditions; 12
0°C x 180 hr S% gear formula testing machine used.

[Effects of the Invention] The flexibility imparting agent for polyamide resin and the polyamide resin composition for molding of the present invention solve the conventional problems of flexibility, impact resistance, and heat aging resistance of polyamide resin after molding. This is a significant improvement.

That is, by reacting a polyamide resin with the flexibility-imparting agent of the present invention, a composition can be obtained in which the hydrogenated conjugated diene polymer, which is a soft segment, is completely incorporated into the polyamide resin. As a result, it was possible to significantly improve the flexibility, impact resistance, and heat aging resistance of polyamide resin after molding, which were problems in the past.

Because of the above effects, the flexibility imparting agent for polyamide resin and the polyamide resin composition for molding of the present invention are suitable for use in molded products such as automobile parts, housings for electrical equipment, and parts used in the electrical and electronic fields. suitable.

Claims (1)

[Scope of Claims] 1. A flexibility-imparting agent for polyamide resin (B) comprising a glycidylated product (A) of a hydrogenated conjugated diene polymer containing a hydroxyl group or a carboxyl group. 2. A molding polyamide resin composition characterized by containing a reaction product of a polyamide resin (B) and a glycidylated product (A) of a hydrogenated conjugated diene polymer containing a hydroxyl group or a carboxyl group. .