JPS6247304A - Soft comb of dryer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a dryer non-7 comb made of polyester elastomer.

(Prior art and its problems) The soft combs of conventional dryers are made of synthetic rubber such as silicone rubber and chloroprene rubber, chlorinated polyethylene, polyester elastomer, ethylene-vinyl acetate copolymer (hereinafter abbreviated as EVA), etc. Although many thermoplastic elastomers have been used, they do not necessarily fully satisfy the properties required for this application.

For example, silicone rubber or chloroprene rubber has low tear strength, cracks during use, is difficult to color, requires a vulcanization process, and has poor productivity, and chlorinated polyethylene, polyester elastomer, and EvA have poor heat aging resistance. However, it is considered to be difficult to put into practical use due to lack of chemical resistance and flexibility.

(Another Means to Solve the Problem) The present inventors have developed a soft comb 8% for a dryer made of polyester elastomer which does not have the above-mentioned defects.
As a result of intensive research, we discovered that polyester elastomer (
The composition is made by blending a modified olefin copolymer with excellent compatibility, and is a practical product that has heat aging resistance, chemical resistance, and high flexibility without losing the excellent properties of polyester elastomer. The present invention was completed by discovering a composition with extremely high performance.

That is, the present invention provides a soft comb for a dryer, which is formed by molding a polyester elastomer composition containing a polyester elastomer and a carboxyl group- and/or epoxy group-containing olefin copolymer. It is something.

The polyester elastomer used in the present invention is a block copolymer with a high melting point node segment mainly composed of alkylene terephthalate units.

A high melting point compound mainly composed of alkylene terephthalate units.
-dosegments include terephthalic acid or its dimethyl nysterst, ethylene glycol, phlopylene f I
J: Examples include those mainly composed of units consisting of I-h, alkylene glycol such as tetramethylene glycol, pentamethylene glycol, 2,2-dimethyl-trimethylene glycol, hexamethylene glycol, decamethylene glycol, etc. Isophthalic acid, 1.5-naphthalenedicarboxylic acid, 2.6-naphthalenedicarboxylic acid, diphenyldicarboxylic acid, bis(p-carboxyphenyl)methane, 4.
, aromatic dicarboxylic acids such as 4'-sulfonyl dibenzoic acid, aliphatic dicarboxylic acids having 2 to 12 carbon atoms, diols such as p-xylylene glycol and cyclohexane dimetatool as glycols, and p-oxybenzoic acid H1p as oxyacids. There is no problem even if a small amount of -(β-hydroxyethoxy)benzoic acid or the like is included as a component.

In addition, as a low melting point soft segment made of aliphatic polyether and/or aliphatic polyester, poly(
polyether glycols such as ethylene oxide) glycol, poly(propylene oxide) glycol, and poly(tetramethylene oxide) glycol; mixtures or copolymers of these polyether glycols;
polyε-caprolactone, a polyester produced from an aliphatic dicarboxylic acid having 2 to 12 carbon atoms and an aliphatic glycol having 2 to 10 carbon atoms, such as polyethylene adipate;
Polytetramethylene acetate, polyethylene sebacate, polyneopentyl sebacate, polytetramethylene dodecanate, polytetramethylene acetate, polyhexamethylene acetate, and polyester polyethers that are a combination of the above aliphatic polyesters and aliphatic polyethers. Examples include polymers.

In such a polyester elastomer, the molecular weight of the low melting point soft segment block is usually 400 to 6000, preferably 400 to 2000, and the proportion of the soft segment in the polyester copolymer is usually 5 to 80% by weight, preferably 20% by weight. ~70% by weight.

These polyester disstomers can be produced by conventionally known normal polycondensation methods. A preferred method is to heat a low melting point soft segment component consisting of terephthal mt or its dimethyl ester, alkylene glycol, aliphatic polyether and/or aliphatic polyester to about 150-250°C in the presence of a catalyst. , a method for obtaining a p1 polyester block copolymer by carrying out an esterification or transesterification reaction, and then carrying out polycondensation while removing excess alkylene glycol under vacuum, a pre-prepared high melting point polyester segment-forming prepolymer and Aliphatic diisocyanates, such as tetramethylene diisocyanate and hexamethylene diisocyanate, which react with the terminal functional groups of those prepolymers to form prepolymers with low melting point polymer segments:
tolylene-2,4-diisocyanate, tolylene-2,
6-diisocyanate, diphenylmethane-4,4'-
Diisocyanates, aromatic diisocyanates such as m- and p-phenylene diisocyanate and naphthalene-1,5-diincyanate; lli diisocyanates such as dicyclohexylmethane diisocyanate; compounds, incyanate compounds such as tolylene diinocyanate dimer, diphenylmethane-4,4'-diisocyanate dimer, β,
t-Epoxypropyl ether, 1,4-bis(β, γ
-Eboxyproboxy)butane, 1,6-bis(epoxyethyl)-hexane, 2,2-bisCp G's
γ-Epoxypropoxy)phenyl]propane, 1-epoxyethyl-3,4-epoxycyclohexane, 1-
(β,γ-epoxypropoxy)-2-benzyloxyethane, 1-(β,r-epoxyproboxy)-2-ethoxyethane, 1,4-bis(β,γ-epoxyproboxy)benzene, etc. There are methods for obtaining modified polyether ester block copolymers and modified polyester ester block copolymers by mixing and reacting glycidyl ether compounds and the like.

On the other hand, in the present invention, a portion of the backbone polymer of the polyester elastomer mixed sulcarboxyl group-containing olefin copolymer is at least 50 mol%, preferably 70 mol% of 1-olefin, ethylene, propylene, butene- 1, Isobutyne, Pentene-1, Hexene-
1, Decene-1,4-methylpentene-1,4-methylpentene-1,4,4-dimethylpentene-1, vinylcyclohexane, styrene, α-methylstyrene, styrene substituted with lower alkyl substituents or similar It is also possible to use mixtures of the above-mentioned olefins. Copolymers obtained from ethylene and butene-1 or propylene are preferred, and commercially available products include, for example, Tafmer A4085, Tafmer A
4090, Tafmer A series such as Tafmer A20090 [ethylene-butene-1 copolymer, Mitsui Petrochemical Products], and Tafmer PO280, Tafmer PO480
, Tafmer PO380 [ethylene-propylene copolymer, Mitsui Petrochemical Industries, Ltd. product] such as Tafmer P0680 and Tafmer PO380.

The above carboxyl group-containing olefin copolymer has α, β
- Manufactured by known methods such as direct copolymerization of an unsaturated carboxylic acid comonomer and the above-mentioned olefin constituting the backbone polymer of the copolymer, or graft copolymerization from the olefin to a polyolefin and polyolefin copolymer obtained. .

Examples of the acid component used here include acrylic acid, methacrylic acid, itaconic acid, (anhydrous) maleic acid, fumaric acid, and monoesters of the above carboxylic acids. Preferably, acrylic acid, Mention may be made of methacrylic acid and (anhydrous) maleic acid. Among these, maleic acid (anhydride) is particularly preferred since it can provide a sufficient acid modification effect even when added in a small amount compared to other acids.As a preferred carboxyl group-containing olefin copolymer, ethylene-butene-1-( anhydrous) maleic acid copolymer, ethylene-pro,
Examples include helene-(H water) maleic acid copolymer.

The epoxy group-containing olefin copolymer can be produced by direct copolymerization of a glycidyl ester of an α,β-unsaturated carboxylic acid with an olefin constituting the backbone polymer of the carboxyl group-containing olefin copolymer, or a polyolefin obtained from the olefin. It is produced by a known method such as graft copolymerization to a polyolefin copolymer.

One or more mixtures of α,β-unsaturated carboxylic acids represented by the formula glycidyl (wherein R is a hydrogen atom or a lower alkyl group) used herein, such as glycidyl acrylate, methacrylic acid, etc. Examples thereof include glycidyl, glycidyl ethacrylate, and among them, glycidyl methacrylate is preferably used.

Such carboxyl group- and/or epoxy group-containing olefin copolymers contain usually 0.01 to 20% by weight, preferably 0.01 to 20% by weight, preferably 0.01 to 20% by weight, as a constituent component of the heptamine having these functional groups.
The content ranges from 0.05 to 5% by weight.

The polyester elastomer composition of the present invention contains a small amount of a mold release agent, a coupling agent, a coloring agent, a lubricant, a weathering stabilizer, a foaming agent, a rust preventive agent, a flame retardant, a flame retardant aid such as antimony trioxide, etc. Other known additives may also be added.

In addition, when carrying out the present invention, other thermoplastic resins or nidistomers, such as polyvinyl chloride, ethylene-acetized vinyl copolymer, polyurethane, styrene elastomer, polybutadiene,
It is also possible to use a vinyl chloride elastomer, acrylic polymer, polyamide, polyimide, polyamideimide, polyphenylene sulfide, etc. in combination.

The compositions of the invention can be prepared in various known ways.

For example, the raw materials are mixed uniformly in advance in a mixer such as a tumbler or Henschel mixer, and then fed into a twin-screw extruder or the like to be melted and kneaded, and then prepared as Beretz I.

The essential components constituting the present invention are a polyester nystomer and the above-mentioned modified olefin copolymer. In the present invention, the blending ratio of the above-mentioned components is preferably ( At/IBl=9515-30/70 (weight ratio),
It is preferably 90/10 to 50,150 (weight ratio).

When the amount of the olefin copolymer added is greater than 70% by weight, flexibility, hydrolysis resistance, etc. improve, but oil resistance, moldability, etc. tend to decrease. Furthermore, if the amount added is less than 5% by weight, flexibility and hydrolysis resistance will be insufficient.

(Effects of the Invention) The soft comb of the dryer of the present invention has extremely high practicality because its constituent polyester copolymer composition has excellent tensile strength, tear strength, and high flexibility.

(Examples) The present invention will be specifically explained below with reference to Examples, but the present invention is not limited only to these Examples.

In addition, parts in the examples mean parts by weight.

Reference Example 1 (Production of carboxyl group-containing olefin copolymer) Ethylene-butene-1 copolymer (Tafmer A409
0) 100 parts, 065 parts of 1,3-bis(tart-butylperoxyglobil)benzene and 1 part of maleic anhydride
parts were mixed uniformly. Next, the mixture was kneaded and pelletized using an extruder set at a cylinder temperature of 220° C. to obtain a carboxyl group-containing olefin copolymer. When the amount of grafted maleic anhydride was measured using an infrared spectrum, this olefin copolymer was found to be ethylene-butene-1 copolymer 1.
It was confirmed that 0.75 parts of maleic anhydride was grafted to 0.00 parts.

This is called a copolymer<1).

Reference Example 2 (Production of olefin copolymer with epoxy group)
Ethylene-butene-1 copolymer (Tafmer A4090)
100 parts of dicumyl peroxide, 0.5 parts of dicumyl peroxide, and 2 parts of glycidyl methacrylate were uniformly mixed.Then, the mixture was kneaded in a twin-screw extrusion machine with the cylinder temperature set at 200°C, and pelletized to produce an epoxy group-containing mixture. An olefin copolymer was obtained. When the graft content of dimethacrylic acid glycidyl ether was measured using a salt-methyl ethyl ketone solution, this olefin copolymer was grafted with 125 parts by weight of methacrylic acid glycidyl ether per 100 parts of ethylene-butene-1 copolymer. It turned out that it was. This is called a copolymer (Ill).

Examples 1 to 6 Polyester elastomer 1r Polyether ester elastomer A layer dI EM 4 manufactured by AKzQ (Netherlands)
00ojUEL-630), copolymer width obtained in Reference Example 1, copolymer (II) obtained in Reference Example 2 and j@
Irganox 1035 (manufactured by Ciba Geikie Co., Ltd.) as a heat stabilizer, and Tinuvin 327 (manufactured by Ciba Geikie Co., Ltd.), a weathering stabilizer, were blended in the proportions shown in Table 1.
The mixture was kneaded at 220°C using a % extruder and pelletized.

The pellet was molded into a test piece using an injection molding machine, and then used to make a test piece with a thickness of 1.571111 and a width of 50 mm.
In order, the size is 100 m in length, and the diameter is 1 at 2 intervals in the vertical direction.
A soft comb for a hair dryer was prepared which had a row of +a+ circular holes and a row of rectangular holes of 7rm length and 21 widths with an interval of 3111!1, alternately separated for 1.5 days.

A specimen measuring 80 meters long and 2+ meters wide was cut from the obtained soft comb, and mechanical strength (tensile properties), flexibility (hardness), tear strength, flexural fatigue resistance, heat aging resistance, and chemical resistance were measured. Ta.

As shown in Table 1, the results showed excellent performance and excellent practicality.

Comparative Examples 1-2 As comparative examples, polyester elastomer (AKZO Co., Ltd. ([)Near, polyether ester elastomer-IArn
A soft comb was prepared in the same manner as in Example 1 using only the following materials (IEM-400, EL-630) and evaluated.

The results are summarized in Table-1.

The test method and measurement method are as follows.

(1) Tensile properties, hardness, tear strength: Conforms to JIS K-6301.

(2) Flexural fatigue test: According to JIS K-6301. (2B, notched, bent 10 times) (A) Heat aging resistance test: Measurement of tensile strength elongation and tear strength at 140° C. after 30 days, and bending fatigue test.

(4) Chemical resistance test: Hair tonic (Shiseido, Brabus) at 26℃7
After soaking for 6 days and then drying at 140° C. for 14 days, the tensile strength elongation and tear strength are measured, and a flexural fatigue test is conducted.

Claims (1)

[Claims] A soft comb for a dryer, characterized in that it is formed by molding a polyester elastomer composition containing a polyester elastomer (A) and a carboxyl group- and/or epoxy group-containing olefin copolymer (B).