WO1993002149A1

WO1993002149A1 - Odorproof coating composition

Info

Publication number: WO1993002149A1
Application number: PCT/JP1992/000895
Authority: WO
Inventors: Teruhito Maruyama
Original assignee: Dow Corning Kabushiki Kaisha
Priority date: 1991-07-15
Filing date: 1992-07-14
Publication date: 1993-02-04
Also published as: JPH0517687A; AU2274992A; JP2536981B2

Abstract

An odorproof coating composition which forms an odorproof coating0film on a substrate to thereby prevent any odor from migrating or adhering to the substrate and in which the odor adherent to the coating film itself can be readily removed by washing with water. The composition comprises 27-78 wt.% of an amino-silicon compound, 2-33 wt.% of a polydiorganosiloxane having terminal hydroxyl groups and a degree of polymerization of 3 to 50, and 17-43 wt.% of a reactive silicone resin, said resin containing a monovalent unit component represented by general formula (I): R3SiO1/2 wherein R represents 1-8C alkyl or aryl and a tetravalent unit component represented by general formula (II): SiO4/2 in a molar ratio of 0.4:1 to 1.8:1 and also containing 2.0-4.0 wt.% of hydroxyl groups.

Description

Specification

Odor-resistant film forming composition

Technical field

INDUSTRIAL APPLICABILITY The present invention is applied to the surface of a substrate to prevent odor transfer or adhesion, and prevents odor transfer to the substrate even when an odorant comes into direct or indirect contact. The present invention relates to a composition for forming an odor-resistant film that forms a water-resistant film.

Background technology

There are various odorous substances in a normal living environment. For example, odors from odorants such as propionic acid, valeric acid, isovaleric acid, butyric acid, and other organic acids from various foods, grasses, trees, animals, and other biological materials directly or by decay. appear. However, when such odors come into direct or indirect contact with an object, the odors penetrate into the tissue and are fixed, so to speak, by ordinary washing with water or washing with aluminum. There are many cases where deodorization cannot be performed sufficiently.

Under the circumstances described above, it is strongly desired to prevent odor transfer or adhesion to many objects. For example, containers for odorous substances, containers for perishable foodstuffs, etc. that can emit odors due to spoilage or deterioration, wall materials that define odor-filled rooms, and arrangements in such rooms It is desired to prevent odor substances from being transferred or adhered to odorous substances as a result of direct or indirect contact with odorous substances in such objects and others. For example, if the transfer or adhesion of such an odor in a container is sufficiently prevented, the odor is not re-transferred to a substance subsequently contained in the container, which is extremely preferable.

The composition for forming an odor-resistant film according to the present invention is based on an object for which odor transfer or adhesion is desired to be prevented, and is applied to the surface of the substrate to form an odor-resistant film. belongs to. Here, the "odor resistant coating" covers the surface of the base material to prevent the odor from transferring or adhering, and the odor transferred or attached to the coating itself can be easily removed. Effectively deodorizes or deodorizes A coating that has the properties of being restored and maintained.

Conventionally, as a deodorizing means for preventing the transfer or adhesion of odor to various objects, a method of applying a so-called deodorant or deodorant to the objects in advance is known. For example, JP-A-63-168171 and JP-A-2-80051 disclose deodorant treatment means for impregnating or attaching a deodorant or the like to a textile product. Have been.

However, such conventional deodorizing treatment means has low deodorant or deodorant durability. For example, when washing with water is performed, the deodorant or deodorant properties are greatly reduced or completely eliminated. And deodorizing treatment is required again.

Disclosure of the invention

INDUSTRIAL APPLICABILITY The present invention can be applied to a substrate to form a suitable film, thereby preventing the transfer or adhesion of odor to the substrate, and furthermore, the film is capable of washing the odor transferred to itself with water. An object of the present invention is to provide a composition for forming an odor-resistant film which can be easily removed by washing.

The composition for forming an odor-resistant film of the present invention comprises: (1) 27 to 78% by weight of an amide-containing gayne compound; (2) a hydroxyl group at a molecular terminal; and a polymerization degree of 3 to 50%. 2 to 33% by weight of a polydiorganosiloxane and 17 to 43% by weight of a (3) reactive silicone resin, and the reactive silicone resin is represented by the following formula (I). A monovalent unit component represented by the formula (E) and a tetravalent unit component represented by the formula (E) in a molar ratio of 0.4: 1-1.8: 1 and a hydroxyl group content of 2.0-4.0% by weight. It is characterized by doing.

Formula (I) R ₃ S iO _1/2

(R represents an alkyl group or an aryl group having 1 to 8 carbon atoms.) Formula (I) S 10

Hereinafter, the present invention will be described specifically.

In the present invention, an amine-containing silicon compound and a polydiorganosiloxane having a hydroxyl group at a molecular terminal and having a specific polymerization degree (hereinafter referred to as “OH silicone oil”) are used. And a specific reactive silicone resin in a specific ratio to form a composition for forming an odor-resistant film.

The amine-containing gay compound used in the present invention is a silane compound or polysiloxane having at least one primary, secondary or tertiary amine group in the molecule. Yes, it is conventionally known as having deodorant properties, and includes those represented by the following formula (m), formula (IV), formula (V) or formula (VI).

Expression (Π)

R ³ a

I

A! NR S i (OR ⁴ ) ₃ — _a

A ¹ : ー H, — CH ₃ ,-CH ₂ CH ₂ NH ₂ ,

R ¹ ——H, aryl group or alkyl group having 1 to 4 carbon atoms

R ² : an alkylene group having 3 to 4 carbon atoms or

R ³ C 1-4 alkyl group

R ⁴ alkyl group having 1 to ⁴ carbon atoms or one SiCH ₃

a integer of 0, 1, 2

Formula (IV)

R

A'N [R ² S i (0 R) ₃ - _a ] 2

A ¹ , R ² , R ³ , R ⁴ and a are the same as in formula (HI)

Equation (V)

R ⁵ : Unsubstituted or substituted monovalent hydrocarbon containing no amine

A ² : -R ⁶ (NH CH ₂ CH ₂ ) _e NHR ⁷

(R ⁶ : alkylene group having 3 to 4 carbon atoms

R ^7: over H or an alkyl group having 1 to 4 carbon atoms e: 0 ≤ e≤ 3 (where e is an integer))

A ³ : -OH, methoxy group or ethoxy group

Range of average values of b, c and d:

1.90 <b≤2.5

0. 0 1 ≤ c≤ l

0 ≤ d≤ Q. 1

(However, 1.90 ≤ b + c + d ≤ 3)

Equation (VI)

R ⁸ ₂ NS IR

R ⁸ : an alkyl group having 1 to 4 carbon atoms

R ⁹ : an alkyl group having 1 to 4 carbon atoms

In the present invention, among the compounds represented by the formula (ΠΠ), the amine-containing gay compounds represented by the following formulas (Wa) and (Wb) are preferable. The formula (W-a)

H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ S iR ^a _m (OR ^b ) _n

Equation 1 b)

H ₂ N (CH ₂ ) ₃ S iR ^a _m (0 R ^b ) _n

C1-C4 alkyl group

R ^b -CH ₃ or C ₂ H ₅

m Integer of 0 or 1

n an integer of 2 or 3 (However, m + n = 3)

Specific examples of the amine-containing gay compound used in the present invention include the following, but are not limited thereto. 3 — [N-aryl-N- (2-aminoethyl)] aminoprovirtrimethoxysilane

N— (2—aminoethyl) 1 3—aminopropylmethyldimethoxysilane

1 1 (3—aminopropyl) 1 1,1,3,3,3—pentamethyldisiloxane 3—aminopropyltriethoxysilane

3—Aminoprovir tris (trimethylsiloxy) silane

α-ω-bis (3-aminopropyl) polydimethylsiloxane

1, 3 —bis (3-aminopropyl) 1, 1, 1, 3, 3 —tetramethyldisiloxane

-3-Trimethoxysilylpropyl-m-phenylenediamine

p-CN- (2-aminoethyl) aminomethyl] phenethyl trimethoxysilane

N— (2—Aminoethyl) 1-3—Aminoprobeltrimethoxysilane

N, N-bis [3- (methyldimethoxysilyl) propyl] ethylenediamine

Jethyltrimethylsilylamine

Dimethyltrimethylsilylamine

A (2—aminoethyl) aminoprovirt methoxysilane

7- (2-Aminoethyl) aminopropylmethyldimethoxysilane Among these, N- (2-aminoethyl) 13-aminopropyl trimethoxysilane and 3-aminopropyltriethoxysilane are particularly preferred. preferable. The content ratio of the amide-containing gay compound in the composition of the present invention is in the range of 27 to 78% by weight. When this content is low, the film formed cannot have sufficient deodorizing or deodorizing properties, while when this content is high, the 0H silicone oil and Reactive silicone resin , The film does not have good film-forming ability.

The 0 H silicone oil used in the present invention is a polydiorganosiloxane in which both ends of the molecule are blocked by hydroxyl groups, and those having a polymerization degree of 3 to 50 are particularly used. With such a polydimethylsiloxane, the viscosity of the composition is appropriate, and good coating properties can be easily obtained. The content of the 0H silicone oil in the composition is in the range of 2 to 33% by weight. When the content of the OH silicone oil is out of this range, the formed film has low durability, and as a result, the state of the film is impaired even by, for example, one washing with water. become.

The reactive silicone resin used in the present invention comprises a monovalent unit component represented by the formula (I) (so-called M unit component) and a tetravalent unit component represented by the formula (IT) (so-called Q unit) Component) in the range of 0.4: 1 to 1.8: 1, and further contains a hydroxyl group in the range of 2.0 to 4.0% by weight. The content of the reactive silicone resin in the composition is in the range of 17 to 43% by weight. When the content is out of this range, the formed film has low durability, and the state of the film is easily deteriorated by washing with water. On the other hand, when the content ratio of the silicone resin is too low, the wettability of the composition to the substrate is low, and a good film cannot be formed.

An appropriate additive can be added to the composition of the present invention as needed. For example, the time required for curing the coating film of the composition can be reduced by blending a curing acceleration catalyst. Examples of such a curing accelerating catalyst include dibutyltin diacetate and dibutyltin dilaurate. The mixing ratio of such a curing accelerating catalyst is, for example, 0 to 2.0% by weight based on the composition. Other additives include fragrances, colorants, fungicides, viscosity modifiers, and the like.

The composition of the present invention can be easily prepared by mixing necessary components and appropriate additives at once, but the components may be mixed sequentially. In this case, there is usually no particular restriction on the order of mixing.

Industrial applicability

The composition for forming an odor-resistant film of the present invention is used by applying a suitable means to the surface of a substrate comprising an object for which odor transfer or adhesion is desired to be prevented, and forming a film. At the time of coating, the composition for forming an odor-resistant film can be diluted with an appropriate organic solvent in order to obtain suitable coatability. As a means for application, means such as a spray method, a brush coating method, a roll coating method, and a dipping method can be used.

The object of the substrate to which the composition for forming an odor-resistant film of the present invention is applied is not particularly limited, and an object made of rubber, plastic, sealant, wood, fiber, inorganic material, or other various substances is used. It can be a substrate. In particular, substances that cause odors penetrate into the interior from the surface and are fixed. As a result, it is extremely feasible to remove objects that cannot sufficiently remove the odor by ordinary surface cleaning. It is effective.

The coating film made of the composition for forming an odor-resistant film of the present invention has curability by the action of OH silicone oil contained as a component. Therefore, it is possible to cure the applied film by leaving it at room temperature.However, in practice, it is preferable to heat the film.For example, the film is cured by heating at a temperature of 150 ° C or less for 10 minutes or less. Can be promoted.

According to the composition for forming an odor-resistant film of the present invention, since the OH silicone oil has reactivity with respect to both the amine-containing gay compound and the reactive silicone resin, these components are integrated. A bonded coating is formed. Since this coating contains an amine-containing gay compound, it has deodorant or deodorant properties by itself and prevents odor from being transmitted, so it must be applied to the surface of the substrate. Thereby, transfer or adhesion of the odor to the substrate is sufficiently prevented. Moreover, this coating has good odor resistance. That is, when the odorant comes into direct or indirect contact with the film, the film itself transfers or adheres to the odor, but this odor is significantly reduced by washing with water. It can be easily removed, and the deodorant or deodorant that is still effective is maintained even after washing with water. Therefore, the odor can be removed by appropriate washing and washing, and the deodorizing property or the deodorizing property is restored. Therefore, it is not necessary to repeatedly perform the treatment of “deodorizing property or deodorizing property”.

BEST MODE FOR CARRYING OUT THE INVENTION

Examples of the present invention will be described below, but the present invention is not limited by these.

Examples 1 to 11 and Comparative Examples 1 to 8

According to the formulation shown in Table 1, a composition for forming an odor-resistant film according to the present invention and a composition for comparison were prepared.

Component A for this composition is an amine-containing gay compound consisting of N- (2-aminoethyl) -13-aminobutyrate trimethoxysilane, and component B is a molecule having an average degree of polymerization of 17 Dimethylsilicone oil having a hydroxyl group at the terminal,

Component C is composed of a monovalent unit component and a tetravalent unit component, and the molar ratio between the monovalent unit component and the tetravalent unit component is in the range of 0.6: 1 to 1.2: 1. An MQ resin containing 2 to 3% by weight of a hydroxyl group and having a solid content of 70% by weight.

A base material was prepared by applying a silicone rubber sealant to a slide glass in an area of 5 × 5 Omm and leaving it to stand at room temperature for 7 days to cure. 1 g of each of the compositions of Examples and Comparative Examples was uniformly applied to the surface of the sealant of the substrate, and left at 25 ° C. for one day for curing to prepare a sample. At this time, the wettability and curability of each sample with respect to the substrate were examined. Table 1 shows the results.

Each of the samples obtained as described above, together with a control sample, which is a substrate to which the composition was not applied, was placed in a closed container containing propionic acid and having a capacity of 200 milliliters and containing propionate. The cells were allowed to stand at 25 ° C for 3 days without direct contact with the acid. After that, when each sample was taken out, the sample of the example had a clearly lower odor than the control sample. In addition, other than the control sample For each sample, the operation of determining the state of the film and the degree of residual odor after washing with tap water for 5 minutes by smell was repeated twice. Table 2 shows the results together with the initial state of the coating.

Example 1 2 '

A composition was prepared and tested in the same manner as described above, except that 3-aminopropyltriethoxysilane was used as the amide-containing gay compound of component A. Table 2 shows the results.

Example 13

A composition was prepared and tested in the same manner as in Example 6, except that dimethylpolysiloxane having a degree of polymerization of 40 to 50 was used as the 0H silicone oil of the component B. Table 2 shows the results.

The evaluation criteria in the above test are as follows.

Wettability

"〇J A state in which a uniform coating film is formed

"△" State with some pinholes but film formed

"X" No coating is formed on the substrate

Curability

"〇" Hardened until the tackiness is lost

"△" Hardened to the extent that some tackiness remains

"X" High tackiness, not cured

Film condition

"〇" State that exists as a good film

"△" Slightly cracked

"X" Large cracks, not a coating table 1

No. Component A Component B Component C Wettability Curability wt¾J fmf ヽ W ¾ ノ

1 Π A 0

o U ο

2 4 U L n U A 0 ο

3 o U 丄 1 Π U ο

4 0 ϋ D n ο

"

D 4 U 6 U q π ο

n

Application b 5 U L U 0 U π η

7 6 5 b 0 Γ)

U

8 o 0 U ύ U Λ ο Example 9 0 U L Ό 9 Π Λ π

10 ί U 丄 ϋ Λ π 丄丄 7/0 u Λ ο ο ο r r

16 0 0 I n u 0 J π

Q D U o n ri 3 0 ο ο q

丄 o υ 0 L ϋ A c η ο, no L 9 1 ο ο

0 c

Ratio D U π π ο

4 2 5 3 5 4 0 〇 △ Comparison 5 6 0 4 0 〇〇

6 3 5 3 5 3 0 〇 Δ Example 7 7 0 3 0 〇〇

8 4 5 3 5 2 0 Δ 〇

9 8 0 2 0 Δ 〇 State of film Degree of residual odor

No.

Before washing 1 time 2 times 1 time 2 times After washing After washing After washing After washing

I Λ Λ Δ o ο

2 Λ A Δ o ο

3 △ Λ Δ o 〇

4 Λ Λ Λ n ο

5 Λ

Table Λ Λ π application 6 π π n n ο

7 π η An

8 π π Example Q ϊ π

1 0 Re π o ο ο

11 D π Π π π

12 π ο o η ο

13 π o ο ο

1 Λ χ x Δ X

2 △ ■ χ Xο Δ Ratio 3 Δ X X mm X

4 Δ X X X X comparison 5 Δ X X 〇 Δ

6 Δ X X Δ X Example 7 Δ X X 〇 Δ

& ― Δ X X 〇 Δ

9 Δ X 〇 Δ

Claims

The scope of the claims

1. (1) 27 to 78% by weight of an amide-containing gay compound; and (2) 2 to 33% by weight of a polydiorganosiloxane having a hydroxyl group at a molecular terminal and having a degree of polymerization of 3 to 50. And (3) 17 to 43% by weight of a reactive silicone resin.

The reactive silicone resin has a molar ratio of a monovalent unit component represented by the following formula (I) and a tetravalent unit component represented by the following formula (E) in the range of 0.4:;! To 1.8: 1. A composition for forming an odor-resistant film, wherein the composition contains 2.0 to 4.0% by weight of a hydroxyl group.

Formula (I) R ₃ S iO _1/2

(R represents an alkyl group or § Li Ichiru group of from 1 to 8 carbon atoms.) Formula (H) S i0 _4/2

2. Claim 1 wherein the amine-containing gay compound is a silane compound or polysiloxane having at least one primary, secondary or tertiary amine group in the molecule. The composition for forming an odor-resistant film according to the above.

3. The odor-resistant film-forming set according to claim 2, wherein the amine-containing gay compound is represented by the following formula (羾), formula (IV), formula (V) or formula (¾). Adult.

Expression (Π)

A'NR'R'S i (OR) ₃ - _a

A ¹ : -H, one CH ₃ ,-CH ₂ CH ₂ NH ₂ , or

One CH ₂ CH ₂ NHCH ₂ CH ₂ NH ₂

R ¹ : —H, ′ aryl group or alkyl group having 1 to 4 carbon atoms

R ² : an alkylene group having 3 to 4 carbon atoms or

R ³ : an alkyl group having 1 to 4 carbon atoms

R: an alkyl group having 1 to 4 carbon atoms or one SiC H ₃

a: Integer of 0, 1, 2

Formula (IV)

R

A'N [R ² S i (0 R) ₃ -a] 2

A ¹ , R ² , R ³ , R and a are the same as in formula (HI)

Equation (V)

R ⁵ : Unsubstituted or substituted monovalent hydrocarbon containing no amine

A ² : — R ⁶ (NHCH 2 CH ₂ ) _e NHR ⁷

(R ^fi : alkylene group having 3 to 4 carbon atoms

R ^7: over H or an alkyl group having 1 to 4 carbon atoms e: 0≤ e≤ 3 (where e is an integer))

A ³ : OH, methoxy or ethoxy group

Range of average values of b, c and d:

1.9 0 <b≤ 2.5

0.0 1≤ c≤ 1

0≤ d≤ 0.1

(However, 1.9 0 ≤ b + c + d ≤ 3)

Equation (VI)

R ⁸ : an alkyl group having 1 to 4 carbon atoms Four

R ⁸ : an alkyl group having 1 to 4 carbon atoms

4. The composition for forming an odor-resistant film according to claim 3, wherein the amine-containing gay compound is represented by the following formula (Wa) or formula (1-b).

Equation (W-a)

H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ S iR ^a _m (0 R) „

Expression — t>)

H _Z N (CH ₂ ) ₃ S iR ^a _m (0 R) _n

^Ra : an alkyl group having 1 to 4 carbon atoms

R ^b : one CH ₃ or one C ₂ H ₅

m: Integer of 0 or 1

n ··· 2 or 3

(However, m + n = 3)

5. The composition for forming an odor-resistant film according to claim 1, wherein the curing acceleration catalyst is blended at a ratio of 0 to 2.0% by weight.