JPH02152902A - Mothproofing agent - Google Patents

Abstract

PURPOSE:To obtain the subject mothproofing agent having high safety, free from volatilization and maintaining inhibitory effect of mite proliferation by using a quaternary ammonium chloride and an amine-based compound as the main components and further blending a polyester block copolymer therewith. CONSTITUTION:The subject mothproofing agent is composed of a compound (e.g. lauryldimethylbenzylammonium chloride) of formula I (R1 is 4-18C saturated or unsaturated alkyl; R2 and R3 are 1-4C alkyl or alkoxy; R4 is 1-4C alkyl, benzyl, etc.; X is halogen, methyl sulfate, phosphate group, etc.), a compound of formula II (R is 2-4C alkyl; Y1 is 8-18C alkyl, -CH2COO-, etc.; Y2-Y4 are -CH2COO-, etc.; X1 is none, H, Na or K; X2-X4 are H, Na or K) and further preferably a polyester block copolymer in a weight ratio of (99.5-50.5):(0.5-20.0):(0-49) and excellent in dry-cleaning resistance.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an insect repellent treatment agent that suppresses the proliferation of house hygiene pests such as mites.

[Conventional technology] DDT and B
Insecticides such as HC were used, but their use was banned in 1971 due to their carcinogenic properties.In recent years, low-toxicity pyrethroids and organic phosphorus agents such as fenitrothion and fenthion have been used as insect repellents. There is.

[Problems to be solved by the invention] However, since these insect repellents are volatile and thermally decomposable, their insect repellent effect disappears within 6 months to 2 years, and when used on rugs and furniture, It has the disadvantage that it is very irritating to the skin when it comes into contact with the skin.

Under these circumstances, there is a desire for a product that is highly safe, non-volatile, and has a long-lasting insect repellent effect.

It is against this background that the present invention aims to provide an insect repellent processing agent that is safer, less volatile, and has a sustained mite proliferation inhibiting effect.

[Means for Solving the Problems] In order to achieve the above object, the present invention has the following configuration. That is, it is an insect repellent processing agent containing as main components a quaternary ammonium salt compound (A) represented by the following general formula (I) and an amine compound (B) represented by the following general formula (n).

General formula (1) In the formula, R1: 04-18 saturated or unsaturated alkyl group Rp, R3: C1-4 alkyl group, alkoxy group R4
: C1-4 alkyl group or unsaturated aliphatic hydrocarbon group, benzyl group X: halogen atom or W, EM ethyl group, methyl sulfate group, phosphoric acid group.

General formula (n)
, -C1-+2 CH2CH2COO- group Y2 , Y3
, Y4 nee CH2C00- group, -CH2CH2CO
O- group, -CH7C1-12C82COO- group X1: None or H, Na, K X2. X3, X4: Indicates H or Na%K.

In addition, in addition to this insect repellent treatment agent, polyester
Addition of the block copolymer (C) improves durability against washing and dry cleaning, and is therefore suitable for the insect repellent processing agent of the present invention.

The present invention will be explained in detail below.

In the present invention, the quaternary ammonium salt compound (A) represented by the general formula (I) exhibits an insect repellent effect, and such compounds include, for example, compounds represented by the following general formula. .

CH3+ [R1-N-CH3I 〉CH3” [R2-N-CH3] ) (CH2・C
H20) Flow H+ [R4-N -(CH2・CH2・O) 7E H]
XCH3 (Here, R4 is a C8 to CII+ alkyl group or unsaturated aliphatic hydrocarbon group, rrt/n = 2 to 4, X represents a halogen atom, methyl sulfate group, ethyl sulfate group, or phosphoric acid group) ( Here, R5 is a C8 to G+8 alkyl group or an unsaturated aliphatic hydrocarbon group, and X is a halogen atom, methyl sulfate group, ethyl sulfate group, or phosphoric acid group) Quaternary ammonium represented by these general formulas Specific examples of the salt compound (A) are shown below.

CHI” words Hff CI-h　　　　” (C1-12cl-120>2H” Hz CH3 / CH3 CH3 C489+ [C4R9-N-C4R9ko 3r- etc.

In the present invention, an amine compound (8) represented by the following general formula (n) is blended with the compound of general formula (I), and this amine compound (B) is a compound of the compound (A).
It has the property of most conveniently controlling the rust-generating effect of the insect repellent without reducing its insect repellent effect.

General formula (n) show.

In the formula, R: C2-4 furkyl group N: Nitrogen atom Yl: C8-18 alkyl group or -CH2CO0- group, -CH2CH2C00-I,
-CH2CH2CH2COO- group Y2, Y3, Y4 -CHpCO0- group, -CH
2CH2COO- group, -CHp CH2CH2CO
O-group x 1 = none or H, Na, K X2, X3, X4: H or N81K.

Specific examples of such compound (B) include, for example:
The following can be mentioned.

Here,
4 alkylene group, X is an alkali metal (Na or K)
shows.

Next, the polyester block copolymer (C
) means a polyether polyester block copolymer, preferably a block copolymer obtained by copolymerizing at least one selected from terephthalic acid and isophthalic acid, and alkylene glycol and polyalkylene glycol. can give.

As alkylene glycol, ethylene glycol,
Examples include propylene glycol, tetramethylene glycol, and decamethylene glycol.

Examples of the polyalkylene glycol include polyethylene gelicol, polypropylene glycol, and their monoethers. The molecule m of these polyalkylene glycols and their monoethers is 400 to 100.
A value in the range of 00 is preferred.

The composition ratio (weight) of the block copolymer is arbitrary regarding terephthalate units and isophthalate units, but it is in the range of terephthalate units / isophthalate units / polyalkylene glycol units = 1/1 to 1/20. is preferable in terms of insect repellent effect and durability.

In the present invention, the compound (A>) exhibits repellency against house hygiene pests, such as mites, and has an effect of inhibiting proliferation. , is a preferable compound from the viewpoint of safety.

Furthermore, the compound (B) is a compound that is extremely effective in suppressing the rust formation of the compound (A).

This prevents the strong rust-generating properties of the compound (A>) against metals such as iron.

In addition, when such a compound (B) is further combined with an alkyl phosphate compound such as octyl phosphate potassium salt or sodium sulfite, the effect of the compound (B) is further enhanced.

In addition, the polyester block copolymer (C) increases the affinity of the compound (A) and the compound (B) for synthetic fibers such as polyester and polyamide, and is suitable for washing with water or dry cleaning, especially for the latter. Provides excellent durability against cleaning. Furthermore, the compound (A)
, the compound (B) tends to migrate due to heat treatment during processing and tends to cause uneven processing, but by adding the polyester block copolymer (C), this migration can be effectively prevented. It has the effect of preventing and uniformly adhering.

The compounding composition of the insect repellent processing agent of the present invention includes the compound (A
), compound (B), and copolymer (C) in a solid weight ratio of (A): (B): (C) = 99.5-50.5: 0.5-20:O ~49
It is preferable to add the compound in a ratio within the range of from the viewpoint of insect repellent effect, rust prevention and durability.

The insect repellent effect of the insect repellent processing agent of the present invention is mainly due to the compound (A>, and if the amount is less than the above range, the effect tends to decrease.The compound (B) and the copolymer (C) are the compound (A>).
A) It exerts the effect of preventing rust generation and migration, and imparting affinity and durability.
The copolymer (C) is preferably blended in an amount of at least 3%, particularly preferably in a range of 5 to 401ffi%. The presence of the copolymer (C) allows the effects of the compounds (A> and (B)) to be exhibited in a well-balanced manner.

The insect repellent processing agent of the present invention can be applied to various molded products such as plastic, wooden, and metal products, but is particularly applicable to mta products, that is, synthetic fibers, semi-synthetic fibers, natural fibers, and mixtures and mixtures thereof. Textile mixed lll1M! It can be applied to textile products such as padded cotton for futons and cushions, backings, underlays or piles for tatami mats and carpets, and fabrics such as knitted fabrics and non-woven fabrics.

Processing methods for coating or impregnating molded products with the insect repellent treatment agent of the present invention include applying the insect repellent treatment agent by dipping, padding, spraying, coating, etc.;
Conventional processing methods such as drying or heat treatment can be applied.

Note that the insect repellent processing agent of the present invention may be incorporated into a molded product. In that case, the usual method of mixing it with a polymer for usual molding (for gold coating), molding, film formation, or spinning is applied.

The insect repellent effect of the insect repellent processing agent of the present invention was evaluated using a feed attraction method.

That is, in a Petri dish with a height of 30an and a diameter of 200M, powdered feed (Nippon Talea CE-2) for breeding mites was spread as evenly as possible, and on top of this, 19 pieces of untreated cotton and 8 pieces of cotton treated with insect repellent were placed. It was expanded to a size of cm x 8 ctn, and one sheet was placed symmetrically on each side.

- Place a 2.8 cm diameter container containing 1.0 g of powdered feed (moisture 15%) that does not contain any mites at a height of 1.4 crn in the center of this rod, and keep it at a room temperature of 25°C ± 2.
After leaving the egg in an incubator adjusted to a humidity range of 70-80% at °C1 and leaving it for 40 hours, the number of mites that moved into the feed in the container was counted using the saline floatation method to determine the repellency rate, and the insect repellent effect was determined. evaluated. The repellency rate was calculated using the following formula. The larger the repellency rate, the more effective it is, but from the viewpoint of practicality, it is preferable that the repellency rate is 40% or more.

Repellent rate (%) = (A-8>/Ax100 where A: number of mites on untreated cotton B: number of mites on insect repellent treated cotton The present invention will be explained below with reference to Examples.

Example 1, Comparative Examples 1 to 2 Lauryldimethylbenzylammonium chloride was used as the compound (A>, disodium salt of ethylenediaminetetraacetic acid was used as the compound (B), and polyester block copolymer (C) The following ingredients were used and mixed to prepare an insect repellent treatment agent.

The proportions of each component were 70% by weight of A, 10% by weight of B, and 20% by weight of C.

[Polyester block copolymer (C)] An acid component consisting of 70 mol% of terephthalic acid and 30 mol% of isophthalic acid as a dicarboxylic acid component, and an alkylene consisting of 80 mol% of ethylene glycol and 20 mol% of diethylene glycol. 30ffiff1 part of polyester resin composed of glycol component and 3,000 molecule ■
A mixture of polyethylene glycol and a 70-layer base was used.

This formulation was dispersed and diluted in water to prepare a processing agent as a 25% aqueous dispersion (Example 1).

Next, as comparative examples, two types of the above examples, (Comparative example 1) in which the component A>is not included and comparative example 2) in which the component (B) is not included, are shown in the following examples. Adjustment was made in the same manner as 1.

These processing agents were sprayed onto futon cotton made of 6 denier, 76 #I polyester fibers. The solid content was 1.0mff1%.

This futon cotton was heat-treated at 160°C.

The evaluation method is as follows.

[Dry cleaning resistance] According to JIS L-0860. "Washing" in the table means dry cleaning.

[Rust prevention] Card machine needles and futon sewing needles that have been washed in a 0.5% salt aqueous solution (20°C) are immersed in an insect repellent solution.
The degree of rust generation was evaluated after being left in the air for 3 days.

Circle mark: No rust occurrence X mark: Rust occurrence An insect repellent treatment agent was prepared in exactly the same manner as in Example 1 using the following compound (A>).

CH3 (Example 2) (CH)・C112・0)2H (Example 4) C489(
Example 5) The repellency of these Examples was evaluated.

Examples 2 to 5 Instead of lauryldimethylbenzylammonium chloride [compound (A)] used in Example 1, (Comparative Example 3)
, alkenylsuccinic acid potassium salt (Comparative Example 4), and guanidine phosphate (Comparative Example 5) were added separately, and the rest were adjusted in the same manner as in the above example.

These halo treatment agents were applied to futon cotton under the same conditions as in Example 1, and the repellency was examined, as shown in the following table.

Example 6, Comparative Examples 3 to 5 Cetyldimethylbenzyl chloride [compound (A)] was 770% by weight. Polyester block copolymer similar to that used in Example 1 [copolymer (C)] was 20% by weight. ω%
, solid content consisting of 10% by weight of the following compound (B) is 25
% aqueous dispersion was prepared to prepare an insect repellent treatment agent (Example 6).

Examples 7 to 9 In place of the compound (B) used in Example 6, Shun prepared insect repellent processing agents in exactly the same manner as in Example 6, using the following compounds.

Next, as a comparative example, trimethylamine was added instead of the compound (B) component in the above examples (Example 7) (Example 8) 7% (Example 9) The insect repellent treatment agent was adjusted by changing the repellency rate and rust prevention rate as shown in the following table, and futon cotton was then treated in the same manner as in Example 1 (Example 10).

This composition was prepared in the form of an aqueous dispersion without adding the copolymer (C), and this was applied to futon cotton (Example 11).

As a result of examining the insect repellency, rust prevention, and dry cleaning resistance of these insect repellent processing agents, they all showed equivalent insect repellency and rust prevention properties before cleaning, but after cleaning, the treatment of Example 11 It was confirmed that the insect repellent properties of the agent were relatively reduced and it fell off from the futon cotton.

Examples 10-11 Ratio of compound (A): (B): (C) of Example 6 Example 12 In Example 1, polyester block copolymer (
Same as Example 1 except that C) is changed to the following.
When the insect repellent treatment agent was prepared, similar to Example 1, good repellency rate (92%), repellency variation (4%), and rust prevention were obtained.

(Polyester block copolymer (C)) Dicarboxylic acid component: 50 mol% of terephthalic acid, 150 mol% of isophthalic acid and alkylene glycol component: 100 mol% of propylene glycol.
It was produced using 60EIfi parts of a mixture of polyethylene glycol with fi part and molecular weight of 6°000 and polypropylene glycol with molecule m of 3°OOO in a weight ratio of 1:1.

Example 13 The target materials for insect repellent treatment were replaced with natural cotton futon cotton and wool futon cotton, and the following insect repellent treatment agents were used for each, and the solid content was 1.5% by weight by spraying.
It was then heat treated at 140°C for 20 minutes.

As a result, the dust mite repellency rate was 76% for cotton futon cotton and 90.5% for wool futon cotton.

When lauryl benzyl ammonium chloride was replaced with lauryl trimethyl ammonium phosphate, the mite repellency rate was 71.5% for cotton and 8% for wool.
The result was 7.8%, and it was found that all of them provided anti-mite properties.

(Insect repellent composition: solid content 20%) Laurylbenzylammonium chloride 56% Copolymer (C) of Example 1 16% Octyl phosphate potassium salt 18% Stearic acid amine salt 10% Examples 14 to 47,
Comparative Examples 6 to 1 In Example 1, instead of compound A, the following general formula (I
), R1, R2, R3, R4, X
Insect repellent processing agents were prepared using the compounds shown in Tables 1 to 3, respectively.

The tick repellency of these insect repellent treatments was evaluated.

General Formula (I) As is clear from the table, the compounds satisfying the general formula (I) of the present invention showed a high repellency rate, but the other compounds had a low repellency rate.

In addition, the repellency rate in the table is expressed as follows.

◎: Repellent rate 70% or more ○: Repellent rate 40 to less than 70% Δ: Repellent rate 20 to less than 40% X: Repellent rate less than 20% Examples 48-71, Comparative Examples 20-38 In Example 9, compound B Instead of, the following - general formula (I
Xl, Yl, X2, Y2, X of the compound represented by I>
Insect repellent processing agents were prepared using compounds in which No. 3, Y3, X4, Y4, and R are shown in Tables 4 to 6, respectively.

The rust prevention properties of these insect repellent processing agents were evaluated.

General Formula (II) As is clear from the table, rust was not observed in the compounds satisfying the general formula of the present invention, but rust occurred in the other compounds.

In addition, in the table, O: No rust occurs... Good rust prevention △: Some rust occurs... Slightly poor +1 minute X: Rust occurs on the entire surface... Poor (effect of the invention) This invention The insect repellent treatment agent has excellent repellency or growth inhibiting properties against household hygiene pests such as dust mites, and has excellent dry cleaning resistance, but it does not irritate the skin and is suitable for use on futons, cushions, etc. It is extremely effective for filling cotton, carpet backing, sheets, etc.

Moreover, in the case of futon cotton, it also has the characteristic of preventing card machines from rusting.

Claims (2)

[Claims] (1) An insect repellent processing agent containing as main components a quaternary ammonium salt compound (A) represented by the following general formula (I) and an amine compound (B) represented by the following general formula (II). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1: C4-18 saturated or unsaturated alkyl group R_2, R_3: C_1-_4 alkyl group, alkoxy group R_4: C_1-_4 alkyl group group or unsaturated aliphatic hydrocarbon group, benzyl group X: halogen atom or ethyl sulfate group, methyl sulfate group,
Indicates a phosphate group. General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R: C_2-_4 alkyl group N: Nitrogen atom Y_1: C8-18 alkyl group or -CH_2COO- group, -CH_2CH_2COO- group, -CH_2CH_2CH_2COO -group Y_2, Y_3, Y_4: -CH_2COO- group, -C
H_2CH_2COO- group, -CH_2CH_2CH_
2COO- group X_1: None or H, Na, K X_2, X_3, X_4: H or Na, K. (2) The insect repellent treatment according to claim 1, wherein the insect repellent treatment agent is a mixture of the compound (A) and the compound (B) with the addition of a polyester block copolymer (C). agent.