JPS6011951B2 - stripping agent composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a release agent composition, and more particularly, a release agent comprising a thermosetting silicone resin emulsion and a fluorosurfactant that forms a uniform release film in an aqueous system. The present invention relates to a composition.

A hardened silicone resin film is formed on the surface of a peeling base material such as a cellulose base material or a plastic base material to facilitate the peeling of these base materials and adhesive substances, or It is well known to prevent these base materials from coming into close contact with each other.

However, since such silicone-based removable coating resins use organic solvents, they pose pollution problems such as air pollution, problems with the handling of hazardous substances such as fire and explosions, and safety and health problems such as deterioration of the working environment. and will be subject to increasingly strict regulations in the future.

In order to overcome the above-mentioned drawbacks, emulsion type releasable silicones have recently been developed. However, the release base material to be coated, especially paper coated or laminated with polyolefin resin such as polyethylene or polypropylene, or hydrophobic resin sheet such as polyolefin sheet or polyester sheet, is coated with release silicone resin emulsion. Labor cost: 0.
When trying to apply a thin film (solid content) for 3 to 2.5 days per coat, repellency occurred on the substrate, making it impossible to form a uniform silicone thin film.

Therefore, a method has been adopted in which various thickeners are used in combination to prevent the repellency of the emulsion on the surface of the substrate and to obtain a uniform thin film.

However, these methods have the fatal drawback that they require the use of a large amount of thickener, which severely impairs the releasability, which is a characteristic of silicone.

However, the object of the present invention is to provide an emulsion-type silicone release agent that eliminates the above-mentioned drawbacks and has excellent release properties equivalent to or better than conventional solvent-based silicone release agents, as well as anti-blocking properties. to provide the agent.

As a result of various studies, the present inventors have found that the above object can be achieved by using a fluorine-based surfactant (B) in combination with a thermosetting silicone resin emulsion, and have arrived at the present invention. It is something.

That is, the present invention resides in a release agent composition comprising a thermosetting silicone resin emulsion (1) containing a fluorine-containing surfactant.

The thermosetting silicone resin which is the solid component of the emulsion (1) constituting the composition of the present invention includes condensation type and addition type polysiloxanes.

Examples of the above-mentioned condensed polysiloxanes include '1}
General formula [However, in the formula, R is a monovalent hydrocarbon group (for example, methyl group, ethyl group, or phenyl group, etc.), and n is 25
It represents the degree of polymerization that corresponds to a viscosity of 500,000 centistokes or more at zero temperature.

An organopolysiloxane having a terminal hydroxyl group represented by the general formula '2' [where R2 is a substituted or unsubstituted monovalent hydrocarbon group (for example, a methyl group, an ethyl group, a propyl group, or a phenyl group)] ), R3 is an alkoxy group (for example, methoxy group, ethoxy group, propoxy group, butoxy group, or phenoxy group, etc.), a is an integer of 1 or 2, and b is an integer of 2 or 3. , and a+b=3 or 4, an integer.

This is a mixed composition consisting of organoalkoxysilane or organoalkoxysiloxane shown in ] and an organometallic compound as a '3' curing catalyst.

On the other hand, addition type polysiloxanes include, for example, (1
"General formula [where RI is a monovalent hydrocarbon group (for example, methyl group, ethyl group, vinyl group, or phenyl group),
and two or more methylpinylsiloxane units are present in one molecule.

× is a hydroxyl group or a vinyl group, and n is as described above. This is a mixed composition consisting of a compound represented by (2) an organopolysiloxane having at least three Si-day groups in the same molecule, and (3) a platinum compound as a curing catalyst.

Here, representative examples of compounds belonging to each of the above components include compound (1), for example, dimethylpolysiloxane having a hydroxyl group at the end;
These include dimethylpolysiloxane/diphenylpolysiloxane copolymer, dimethylpolysiloxane/dimethylpolysiloxane copolymer, and the like.

Representative examples of compound (2) include trimethoxymethylsilane, dimethoxydimethylsilane, triethoxymethylsilane, triethoxyethylsilane, trimethoxypropylsilane, trimethoxybutylsilane, trimethoxyphenylsilane, and dimethoxyphenylsilane. Examples include enylmethylsilane, dimethoxydiphenylsilane, triethoxyphenylsilane, tripropoxyphenylsilane, diethoxyphenylmethylsilane, dimethoxyphenoxyphenylsilane, and partially hydrolyzed products thereof.

Typical examples of the compound (3) include dibutyltin dilaurate, dibutyltindiolate, lead naphthenate, zinc laurate, and zinc oleate.

Examples of compounds belonging to compound (1') include dimethylpolysiloxane having pinyl groups at both ends or dimethylpolysiloxane having two or more vinyl groups in the side chain and hydroxyl groups at both ends. It will be done. Examples of compounds belonging to compound (2) include methylhydrogenpolysiloxane, methylhydrogenpolysiloxane/dimethylpolysiloxane copolymer, and methylhydrogenpolysiloxane/diphenylpolysiloxane copolymer.

Furthermore, compounds belonging to the compound (3') include inorganic platinum salts such as platinum chloride or chloroplatinic acid, and various types thereof.

These three condensed or addition type ZO components are separately prepared in proportions suitable for peelability, and then
It is coated on a peelable substrate and then subjected to a heat curing treatment to form a peelable coating film. Here, the mixing ratio of each component is such that the compounds (2) and (3) are respectively 0.1 to 10 parts by weight per 100 parts by weight of the compound (1), and on the other hand, In proportions such that, relative to 10 parts by weight of compound (1'), compound (2') is 0.1 to 5 parts by weight, and compound (3') is 0.005 to 0.015 parts by weight as platinum. be.
20 Thus, the thermosetting silicone resin emulsion, which is one of the constituent components of the composition of the present invention, contains the compound (1), (2) or (3).
), or compound (1'), (2) or (3'
) are each type, or two or more types that do not react with each other.
2S039 ■ C8F, 3S02NCH2CH2CH2N(CH3)2
CH2CH20th C7F, 5CH20 (CQC day 20th day 9HC, Zu3, CH20(CH2CH20th day 2nd rainbow CF3
C(C2F5)2C(CF3)=C(CF3)○(CQ
C day 20 na, 50C ratio C,. F23CH20 (CH2C
H20÷7SQNaC8F,7S02N(C2&)(C
40 na for 2 days.

HC7F, 5CON (C2 day 5) (CQC day 20 na 9H
C6F, 3CH2CH2CH (COOH) 2 converting agent and/or
Alternatively, it is emulsified by a conventional method using an anionic emulsifier. On the other hand, the other component of the composition of the present invention, the fluorine-based surfactant track J, is a nonionic, anionic, cationic, and amphoteric surfactant whose hydrophobic group has a carbon number of C6 to C32. This refers to surfactants that account for 2% or more by weight of fluorine atoms in these surfactants, and representative examples include C7F, 5
Examples include COOK, C8F, and 7S08K.

The amount of this fluorine-based surfactant 'B} used is 0 parts by weight for 10 parts by weight of water in the thermosetting silicone resin emulsion.
．． 0.01 to 1 part by weight, preferably 0.05 to 3 parts by weight.

When applying a coating liquid in which the amount of the above-mentioned activator {B) is less than 0.01 part by weight as defined above to a release substrate, no repellency phenomenon occurs on the substrate. If the amount is within the above range, a sufficient effect of preventing the repelling phenomenon will be achieved.

The addition of this fluorosurfactant 'B} to the thermosetting silicone resin emulsion
This may be done either during emulsification or when preparing a coating solution using the composition of the present invention.

In addition, for the purpose of further improving the film-forming properties of the composition of the present invention, for example, polyvinyl alcohol/methyl cellulose, starch, aqueous acrylic resin, aqueous vinyl acetate resin, aqueous ethylene/pinyl acetate copolymer resin, or aqueous styrene/ There is no problem even if a ptagene copolymer resin or the like is used in combination.

Furthermore, when the composition of the present invention is applied as a coating liquid to a release base material, the coating composition may be applied depending on the type of release base material, the coating process, the coating machine, or the use of the coated product. The concentration of the silicone resin in the coating solution and the solid content of the silicone resin in the coating solution are successively adjusted. In the present invention, the above-mentioned "base material for release" includes "for example, paper and plastic film, but in addition, natural or synthetic fibers or their green fabrics, glass cloth, asbestos, asbestos fabrics, etc. may be used as the target material for release." Becomes wood.

The composition of the present invention thus obtained is applied to the above-mentioned release base material and heat cured to obtain excellent releasability against adhesive substances and the release of the base material itself.

It is possible to impart anti-sticking effect. In order to apply the composition of the present invention to a release substrate, known and commonly used coating means can be applied.

For example, coating can be carried out by a coating method using a coating machine such as a roll coater or an air knife coater, by a dipping method, or by a spraying method. Further, the coating amount is preferably 0.3 to 5 coats/me based on the solid content of the thermosetting silicone resin. The heat curing treatment conditions are usually 150 oo x 2 calm sand to 200 qC x 1 inkstone sand or more. Next, the present invention will be explained in detail using examples.

In the following, all parts and percentages are based on weight unless otherwise specified. Example 1 and Comparative Examples 1 to 3 Viscosity at 25°C (hereinafter the same) is 10000000
A copolymer of dimethylpolysiloxane and methylvinylsiloxane that is centistokes and has hydroxyl groups at both ends of the molecular chain (methylvinylsiloxane unit 1.
25 parts of an aqueous emulsion containing 30% of
1 part of an aqueous emulsion containing 50% methylhydrogen polysiloxane having a viscosity of 0 centistokes, 0.005 part of chloroplatinic acid, and a fluorine surfactant c8F,7.
The composition of the present invention was prepared by diluting 0.1 part of so2N (cH2cH2) with water to a total of 10 parts.

For comparison, a case in which C8F・7S02N (CH2CH2o key day was not used at all with a fluorine-based surfactant (Comparative Example 1) and a case in which a hydrocarbon-based surfactant was used instead of this fluorine-based surfactant) were used. C8 day/7S02N (when 0.1 part of CH2CH2o key day is used (comparative example 2) and 3 parts of polyvinyl alcohol [using "Gohsenol NH-20" manufactured by Nippon Gohsei Co., Ltd.] in addition to the formulation of this comparative example 2) A comparative control composition was also prepared in the same manner as the composition of the present invention when (Comparative Example 3) was used in combination with (see Table 1).

These four types of compositions (treatment liquids) were applied onto a kraft paper film with a thickness of 20 mm thick so that the siloxane layer would be 0.8 mm thick, and then 16 mm thick.
A polysiloxane film was formed by heating and curing for 3 minutes at 0oo.

After that, an acrylic resin adhesive tape and a styrene-butadiene rubber (SBR) adhesive tape were attached to the surface coated with this polysiloxane film at a temperature of 70°C.
After crimping for 20 hours at a pressure of 20 k9/m, the peel resistance was measured at a peel rate of 30 skin/min and 20 m/min, respectively.

(This peel resistance value is generally measured using a "180 degree peel test.")
It is called. ) Also, in order to compare the degree of flocking, a temperature of 50°C was measured between the treated surfaces immediately after the formation of the cured film.
After applying a pressure of 80k9/mm and crimping between the two, the peeling resistance was measured in the same manner (however, the peeling rate was 30 arc/min).

These measurement results are summarized in Table 2.

Table 1 (Unit: parts by weight) Table 2 (Unit: 2.5 kg) From the results in Table 2, it can be seen that in the case of Comparative Examples 1 and 2, a repellent phenomenon occurred, and there were areas where the coating was possible and areas where it was not. Therefore, it could not be evaluated in the peel resistance test.

Furthermore, in a comparison between Example 1 and Comparative Example 3, Example 1 was superior to Comparative Example 3 in terms of releasability and flocking property.

Example 2 and Comparative Examples 4 to 5 25 parts of an aqueous emulsion containing 30% dimethylpolysiloxane, which has hydroxyl groups at both ends of the molecular chain and has a viscosity of 5,000,000 Stokes, and 50% dimethyltetraethoxy disiloxane. 1 part aqueous emulsion containing 1 part dibutyl tin dilaurilate and 10% dibutyl tin dilaurilate
3 parts of an aqueous emulsion containing 3 parts of an acrylic resin [methyl methacrylate butyl acrylate/acrylonitrile/3-hydroxyethyl methacrylate = 50/3
3% of an aqueous emulsion containing 50% of a copolymer with a monomer composition (weight ratio) of 8/8/3/1 and 0.1 part of a fluorine-based surfactant were mixed with water for 10 minutes. The composition of the present invention was prepared by diluting it to .

For comparison, when 3 parts of "Gohsenol NH-20" was used instead of the above fluorosurfactant (
Comparative Example 4), and as a solvent system, 7.5 parts of the above dimethylpolysiloxane and the above dimethyltetraethoxy.
An organic solvent solution prepared by diluting 0.5 parts of disiloxane and 0.3 parts of dibutyltin dilaurate with toluene by 10 parts (Comparative Example 5) was prepared in the same manner as the composition of the present invention. A comparative composition was obtained (see Table 3).

These three types of compositions (treatment liquids) were applied separately to the waist of kraft paper made by pasting a polypropylene film with a thickness of 15 mm.
The siloxane was applied at a rate of 1.0 m/m and then heated and cured at 170°C for 20 seconds to form a polysiloxane film. Thereafter, the three types of cured coating films thus obtained were treated in the same manner as in Example 1.
Table 4 summarizes the results of measuring the peel resistance against adhesive tape and the peel resistance due to blocking. Table 3 Table 4 (Unit / 2.5 kg) Reference Examples 1 to 3 As a base material in place of kraft paper coated with a thin layer of polyethylene (Example 1) and a thin layer of polypropylene (Example 2) Using glassine paper, polyester film, and aluminum foil, and using the composition obtained in Example 2, the same operation as in Example 2 was carried out to form a polysiloxane film, and then the cured coating thus obtained was The peel resistance of the film to the adhesive tape was measured in the same manner as in Example 1, and the results shown in Table 5 were obtained.

Table 5 2.5 units)

Claims (1)

[Claims] 1. A release agent composition comprising a thermosetting silicone resin emulsion (A) and a fluorosurfactant (B).