KR100535439B1 - Composition of releasing agents for dispersion based-on silicone - Google Patents

Abstract

The present invention relates to a silicone dispersion release agent composition, and more particularly, to a silicon dispersion release agent composition containing a specific amount of silicone resin, silicone oil, fumed silica and platinum catalyst. The composition of the present invention has a low reduction of the residual adhesion rate, low retention of low release force, air exposure resistance, good adhesion with a plastic film, and can provide a uniform silicone cured coating film as well as a solvent-free type and a solvent type. Genie has excellent performance that satisfies the advantages.

Description

Silicone dispersion release agent composition {COMPOSITION OF RELEASING AGENTS FOR DISPERSION BASED-ON SILICONE}

The present invention relates to a silicone dispersion release agent composition, and more particularly, to a silicon dispersion release agent composition containing a specific amount of silicone resin, silicone oil, fumed silica and platinum catalyst. The composition of the present invention has a low reduction of the residual adhesion rate, low retention of low release force, air exposure resistance, good adhesion with a plastic film, and can provide a uniform silicone cured coating film as well as a solvent-free type and a solvent type. Genie has excellent performance that satisfies the advantages.

Silicone dispersion releasing agent has a siloxane bond and has excellent properties in various aspects such as heat resistance, weather resistance, and chemical stability. The bond energy of the siloxane structure is large, but unlike the carbon-carbon bond, because the helical structure has a small intermolecular force, an organic silane-based adhesion promoter is used to give adhesion because it is a resilient material having a high elasticity and a high compressive force. (Reference: 2002 New Technology Trend Report-Silicone Polymer-KIPO)

The silicone dispersion releasing agent is used for a wide range of purposes from general fields such as general labels and food packaging to specialty fields such as industrial bar codes and pharmaceuticals. Today, the demand for stability against environmentally friendly aspects, such as VOC regulations and ISO14000, as well as environmental hazards such as environmental hormones, is increasingly regulated and requires rigorous testing standards.

Recently, the shape of the silicone dispersion releasing agent is also showing a great change in Korea. Although the solvent type was the mainstream, it has been changed to the solventless type in terms of safety and hygiene and environmental protection. However, in order to coat the solvent-free dispersant release agent, it is necessary to add equipment such as a coater that satisfies the solvent-free type, which requires a large amount of initial equipment, and the conventional solvent-free dispersant release agent does not adhere to the plastic film and can be coated. The thickness is non-uniform, and the technology is not precisely used for consumers.

In practice, the solvent type coating is performed in a very thin area of 0.3 μm (0.3 g / m 2) or less, but the solvent type is applied in an area of 1.0 μm (1.0 g / m 2) or less.

The type and content of silicone resin, silicone oil, silica, organosilane, inorganic metal compound additives, and the like, which are added in the preparation of the solvent-free silicon dispersion release agent, are very important. The following is a summary of the prior art.

(1) low-viscosity organosilicon oils containing hydrocarbon radicals containing one or more alkenyl functional groups of lower bicyclo (ie linear and branched alicyclic) and one or more hydrogen functional groups The release composition by addition bonding of the organosilicon oil, including the coating film has a higher hardness than the solvent type, provides a low release force when releasing at high speed, but does not adhere to the plastic film. It is difficult and the curing temperature is over 100 ℃. (Reference: Tsu Rico-Sono 應用-東京 芝 浦 電氣-ツ リ コ-ソ (株), 1988)

(2) Toluene, which is a petroleum-based solvent, in an organosilicone oil containing at least one higher alkenyl functional group and an organosilicone oil containing at least one hydrogen functional group having a viscosity at 25 ° C of 0.1 to 1 poise or more. Xylene) and a nucleic acid in a ratio of 1: 1, and the composite composition prepared by adding 5 to 20% by weight of fumed silica and 1 to 2% by weight of the organometallic compound as an additive provides a composition having a relatively low release force. do.

However, depending on the amount of hydrogen bonded to the silicon atom of the hydrogen-sensitive silicone oil, the curing rate is generally slow up to 30 to 60 seconds. In particular, when the hydrogen content is excessive, it penetrates into the adherent material and separates from the release composition in the dry curing step (migration, miglation), and the excess hydrogen functional silicone oil is cured by itself, resulting in an uneven coating surface. (Note: ツ リ コ-ソ 活用 技術-情報 技術 協會)

(3) The trichlorophenylsilane and the 3-aminopropyltriethoxysilane were mixed and then hydrolyzed using toluene, and then the composite composition using dibutyl dilaurate and flame retardant as a curing catalyst was excellent in high speed curing and heat resistance. It is necessary to control the by-products, and it is difficult to control the peeling characteristics. (Refer to USP5281656 et al.)

(4) Silicone compositions comprising trimethylsiloxy terminated organopolysiloxanes and organopolyhydrogensiloxanes containing two or more alkenyl groups having four or more carbon atoms per molecule, and a platinum catalyst as a curing agent have excellent peeling force, preferably In addition, it is excellent in low release properties and provides an expensive release force at a high peeling amount. However, this composition may be changed to expensive release force after a certain period of time (see USP4087399, USP4678827 et al.).

(5) using an organic siloxane, organometallic compound, toluene and nucleic acid, ethyl acetate containing a polysiloxane containing a halogen atom or a cyano group and a hydrocarbon radical containing phenyl to alkenyl, and a solvent in a ratio of 2: 2: 1 The composite composition can be cured at high speed, but has a disadvantage that the curing temperature is very high (see USP5036117 et al.).

SUMMARY OF THE INVENTION An object of the present invention for solving the above problems is to provide a silicone dispersant release agent composition with less reduction in residual adhesion and improved retention of low release force.

In addition, another object of the present invention is to provide a silicone dispersion release agent composition which is excellent in adhesion with a plastic film and capable of uniform coating.

In addition, another object of the present invention is to provide a silicone dispersion release agent composition capable of increasing the molding rate of the plastic film, improving the air exposure resistance, and forming a silicone cured coating film without a transfer phenomenon.

In order to achieve the above object, the present invention

3 to 5% by weight of silicone resin,

70-85 wt% of silicone oil,

3-10 wt% of fumed silica, and

It provides a silicon dispersion release agent composition containing 1 to 5% by weight of the platinum catalyst.

Hereinafter, the present invention will be described in more detail for each component.

(1) silicone resin

Silicone resin which is the first component of the present invention is as shown in the following formula (1).

The silicone resin is commonly known as an organopolysiloxane resin, and the silicone resin (MQ) is a polymer composed of R ₃ SiO _1/2 (M units) and SiO _4/2 units (Q units). to be. In this case, R is a functional or non-functional functional group, and may optionally include a portion of R ₂ SiO _2/2 and R ₁ SiO _3/2 units, which are called D and T units, respectively. MQ resins referred to in the present invention mean that on average only 20 mole percent of the resin molecules comprise D and T units.

In the present invention, the silicone resin serves as a crosslinker for bonding them to each other between the silicone oil and the silica, and is dispersed in the silicone oil and mainly relates to adhesion, flexibility, elasticity, and the like.

The main factors for determining the properties of the silicone resin are the number average molecular weight (Mn) of the resin and the ratio of the M unit and the Q unit, the content of the reactor of the silicone resin. The Mn of the silicone MQ resin generally used is 1,000 to 10,000, preferably 3,000 to 7,000, more preferably 3,500 to 6,500. At this time, the molar ratio of M unit: Q unit of the silicone resin is 0.5: 1 to 1.3: 1, preferably 0.5: 1 to 1.1: 1, more preferably 0.5: 1 to 1.0: 1. The concentration of the reactor is 1 to 20 mol%, preferably 1 to 10 mol%, more preferably 1 to 6 mol% or less.

In this case, when the ratio of the M unit: Q unit has a value lower than 0.5, the adhesion of the coating film is inferior, and when the value is higher than 1.3, cracks are generated on the surface of the coating film. In addition, the reactor of the silicone resin also has a great influence on the physical properties of the dispersion, and the more the reactor of the silicone resin in this way, the flexibility of the coating film is improved.

In consideration of the above matters, the silicone resin used in the present invention has a content of 3 to 5% by weight based on the total composition.

(2) silicone oil

The second component of the present invention, silicone oil, serves as a main binder for silicone varnishes, and contains higher cycloaliphatic and non-cycloaliphatic (ie linear or branched aliphatic) epoxy polysiloxanes, halogen atoms or cyano groups. Organosiloxanes containing polysiloxanes and hydrocarbon radicals containing phenyl or alkenyl and the like are used.

In this invention, vinyl group polysiloxane and hydrogen polysiloxane are mixed and used, The mixing ratio of the vinyl group and hydrogen group in the said polysiloxane is good to mix in 1: 1.5-3.0 molar ratio. That is, by using an excess of the hydrogen group compared to the vinyl group it can promote the crosslinking of the two working periods to promote the residual adhesion rate. When the hydrogen group mixing ratio of the polysiloxane is less than 1.5, an uncured reactant is generated and hardening is not performed, resulting in poor adhesion to the plastic film and a decrease in the residual adhesion rate. When the polysiloxane exceeds 3.0, hydrogen gas is generated by mutual reaction of hydrogen groups. Is generated to pass through the coating film, the appearance of the coating film is poor.

Examples of the vinyl group polysiloxane include polydimethylsiloxane (Formula 2), polymethylvinylsiloxane (Formula 3), polyfluoromethylvinylsiloxane (Formula 4), polyphenylvinylsiloxane (Formula 5), and the like. A (Mn) of 100,000 to 500,000, preferably 100,000 to 300,000, and a viscosity of 100 to 10,000 cps can be used. Such vinyl-based polysiloxanes are used differently depending on their use, and methylphenylvinyl polysiloxane, oil-resistant methylfluoroalkyl polysiloxane, etc. may be used for heat resistance and cold resistance.

In addition, the hydrogen polysiloxane may be, for example, methylhydrogen polysiloxane (Formula 6), hydrogen end-capped polysiloxane (Formula 7), copolymerized methylhydrogen polysiloxane (Formula 8), and the like, which may be used as a methylene under a platinum compound It is formed by a bond. The molecular weight (Mn) of the hydrogen polysiloxane is 100,000 to 500,000, preferably 100,000 to 300,000, more preferably 100,000 to 200,000, and a viscosity of 10 to 1,000 cps may be used.

      The silicone oil used in the present invention is used in 70 to 85% by weight, if the amount of use is less than 75% by weight cracks in the coating film and when the content exceeds 85% by weight, the retention rate of the low release property of the coating film is reduced do.

(3) fumed silica

Fumed silica, the third component of the present invention, has a particle size of at least 16 nm or less, and has a minimum specific surface area (BET method) of 200 m ² / g or more to facilitate dispersing (dispersion) and to obtain a coating. Increase the flexibility and elasticity of the coating.

The fumed silica used at this time is used after the surface treatment, and the surface treatment is performed by treating the fumed silica with an organosilane, an organosiloxane, an organosilazane, an organosilicon compound, and then again with a titaniumate compound. Preferably, the surface-treated fumed silica is used by surface treatment again with a titaniumate compound.

The fumed silica used in the present invention may be 3 to 7 wt% based on the total composition in consideration of the dispersion and coating coating properties of the composition.

(4) platinum catalyst

Platinum catalysts, which are the fourth component of the present invention, are commonly used as curing accelerators, and have excellent effects such as flame retardancy, heat resistance, and electrical insulation.

In the present invention, (ethylene) bis (triphenylphosphine) platinum (Pt {P (C ₆ H ₅ ) ₃ } ₂ (C ₂ H ₄ )) is synthesized with a platinum catalyst, and the synthesized platinum catalyst isopropyl alcohol. Disperse in and use. The platinum catalyst improves self-extinguishing property and excellent compatibility with silicone oil, so that it is well dispersed in the silicone oil. Thus, the platinum catalyst not only enhances the curing rate but also does not separate the silicone oil and improves storage stability.

In the present invention, the synthesized platinum catalyst (ethylene) bis (triphenylphosphine) platinum (Pt {P (C ₆ H ₅ ) ₃ } ₂ (C ₂ H ₄ )) alone or using the following phosphate-based platinum One or more types can be selected and used out of a compound. Examples of phosphoric acid-based platinum compounds include Pt {P (OC ₆ H ₅ ) ₃ } ₄ , Pt {P (C ₆ H ₅ ) ₃ } ₄ , Pt {P (CH ₃ ) ₃ } ₄ , Pt {P (C ₄ H ₉ ) ₃ } ₄ , Pt {P (OCH ₃ ) ₃ } ₄ , Pt {P (OC ₆ H ₅ ) ₃ } ₄ , Pt {P (C ₆ H ₅ ) ₃ } ₃ , Pt {P (C ₆ H ₅ ) (C ₂ H ₅ ) ₂ } ₄ , Pt {P (OC ₆ H ₅ ) (OC ₂ H ₅ ) ₂ } ₄ , Pt {P (C ₆ H ₅ ) ₂ (OC ₂ H ₅ )} ₄ And Pt {P (CH ₃ ) ₂ (OC ₄ H ₉ )} ₄ .

The platinum catalyst is preferably used in an amount of 1 to 5% by weight, preferably 1 to 3% by weight, and in the case of using a large amount exceeding the above range, bubbles are formed in the coating film due to the too fast curing speed. The surface may not be uniform and the reduction of residual adhesion may increase, and black spots may partially appear on the coating film due to oxidation of the platinum catalyst itself, which may result in yellowing.

The platinum catalyst synthesized in the present invention was prepared by preparing Pt {P (C ₆ H ₅ ) ₃ } ₂ (CO ₃ ) as a precursor and then synthesizing it using the precursor, and the synthesis thereof will be described in detail below. .

Pt {P (C ₆ H ₅ ) ₃ } ₂ (C ₂ H ₄ ) Synthesis

The _{Pt {P (C 6 H 5} ) 3} 2 (C 2 H 4) as a precursor for the synthesis of _{Pt {P (C 6 H 5} ) 3} 2 (CO 3) was synthesized. 5 g (4 mmol) of Pt {P (C ₆ H ₅ ) ₃ } ₄ was dissolved in 120 mL of benzene, and the dissolved solution was bubbled with CO ₂ and O ₂ gas for about 30 minutes. The mixture is very dark yellow. The solid was filtered using a medium pore filter, which was washed with 50 mL of benzene, dissolved in 75 mL of dichloromethane, and 5 g (19 mmol) of triphenylphosphine was added thereto. The mixture was refluxed for at least 12 hours and 75 mL of benzene was added and then evaporated until the total volume was halved. After filtration using a medium pore filter, a solid was obtained, washed with 50 mL of benzene and 25 mL of ethanol, and then the washing solution was evaporated to obtain a precursor.

In a 100 mL Two-neck flask, 1.5 g (1.75 mmol) of Pt {P (C ₆ H ₅ ) ₃ } ₂ (CO ₃ ) was dissolved in 40 mL ethanol, and a dropping funnel was fixed to one neck. On the other side, the tube was connected so that ethylene gas could reach the surface of the mixture. 20 mL of 0.1M sodium tetrahydroborate (NaBH ₄ / Ethanol) was added to the dropping funnel and added dropwise over 20 minutes with vigorous stirring. At this time, ethylene gas was continuously injected. After filtration through a medium pore size filter, a solid was obtained, washed in the order of 20 mL of ethanol, 25 mL of H ₂ O and 25 mL of ethanol, evaporated and dried in vacuo to give a pale yellow Pt {P (C ₆ H ₅ ) ₃ } ₂ (C ₂ H ₄ ) was obtained. IR data of Pt {P (C ₆ H ₅ ) ₃ } ₂ (C ₂ H ₄ ) obtained above is shown in FIG. 1 (yield: 70%)

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Examples 1-3 and Comparative Examples 1-3

To the composition shown in Table 1, the silicon dispersion was prepared in a two-part type, and the same method was performed as follows.

First, additives such as silicone resin and fumed silica were dispersed and dispersed in silicone oil to prepare an uncured compound (PART-A). The platinum catalyst (PARTB) synthesized in the prepared uncured compound (PART-A) was added and dispersed sufficiently, followed by a defoaming process, and coated on a plastic film with a thickness of 0.3 μm (0.3 g / m 2), followed by hot air drying at 80 ° C. Specimens were prepared by curing in a circulation oven for 15 seconds. Subsequently, the specimen was left to stand in a constant temperature and humidity chamber at 25 ° C. and 50% relative humidity for 24 hours to prevent the phenomenon of low release force retention rate degeneration.

Classification (% by weight) Example Comparative example One 2 3 One 2 3 Silicone resin ¹⁾ 5 5 5 5 5 5 Silicone oil Methylvinylpolysiloxane ²⁾ 81 81 81 81 81 81 Methylhydrogen copolymerized polysiloxane ³⁾ 4 4 4 4 4 4 Fumed silica 7 8 7 7 8 7 Platinum catalyst A ⁴⁾ - - One - - - B ⁵⁾ 3 2 2 - - - C ⁶⁾ - - - 3 2 One D ⁷⁾ - - - - - 2 1): M: Q = 0.85: 1, number average molecular weight 5,0002): viscosity 10,000 cps, molecular weight 250,000, vinyl group content: 2 mol% 3): viscosity 50 cps, molecular weight 250,000, hydrogen group content: 4.2 mol% 4): Pt {P (C ₆ H ₅ ) ₃ } ₄ 5): Pt {P (C ₆ H ₅ ) ₃ } ₂ (C ₂ H ₄ ) 6): Pt {P (C ₆ H ₅ ) (C ₂ H ₅ ) ₂ } ₄ 7): Pt {P (CH ₃ ) ₂ (OC ₄ H ₉ )} ₄

Test Example 1

In order to determine the physical properties of the specimens prepared in Examples and Comparative Examples was carried out as follows.

1. Adhesion of Coating Coating Film

Each of the specimens was rubbed by hand at 25 ° C. to confirm the dropping of the coating surface. The coating surface was washed out. At this time, the thickness of the coating film was used as the thickness of 0.3 ㎛ (0.3 g / ㎡) as described above, the measuring instrument used QUV 313B ((US) Q-PANEL). The results obtained in this test are as shown in Table 2 below, and the measured data values indicate the number of specimens unsatisfactory in the test, each of 10 specimens in a bundle.

division Example Comparative example One 2 3 One 2 3 Adhesion Dropout 0 0 0 5 4 4 Coating film blurring phenomenon 0 0 0 5 6 6

2. Silicone coating uniformity

The silicon coating thicknesses were all measured by a 0.3 μm (0.3 g / m 2) one using a silicon coating meter (X-LAB 3000, Oxford Co., Ltd.), and the results are shown in Table 3 below. In addition, the uniformity of the coating surface was observed by an electron microscope.

division Example Comparative example One 2 3 One 2 3 Coating surface uniformity Good Good Good Bad Bad Bad

3. Air exposure

The air exposure resistance was left to stand for 500 hours in the QUV to confirm whether the surface of the specimen yellow progress, the results obtained are shown in Table 4 below. At this time, the silicon coating thickness used was 0.3 ㎛ (0.3 g / ㎡), all 12 specimens were placed in the QUV chamber and left for 500 hours to check whether yellowing occurred on the coated surface of the specimen. QUV 313B (Q-PANEL) was used. The obtained measured data values indicated that the number of specimens dissatisfied with the test was made with one bundle of ten specimens each.

division Example Comparative example One 2 3 One 2 3 QUV test 0 0 0 10 8 9

4. Release force and residual adhesion rate

The release force and residual adhesion rate were tested according to the FINAT standard. Specifically, the specimen size of the release force and the residual adhesion rate is the same as the 20 × 100 × 0.4 (mm) plate shape, using the adhesive tape {3M Scotch 610 tapes; Manufacturer: 3M (3M)} and maintained in a constant temperature and humidity room at 25 ℃, 50% relative humidity for 24 hours, the adhesive tape of the specimen was floated at a rate of 180 °, 12 in / min. In this case, an Adhesion release tester {AR-2000, (US) Chemstrustrument Co., Ltd.) was used as a measuring device, and the obtained results are shown in Table 5 below.

In addition, the residual adhesion rate is the same as No. 2 by applying the above-mentioned standard adhesive tape on the stainless steel plate, then the adhesive force is 100, and the outstanding adhesive tape after the release force measurement is repainted on the stainless steel plate. The value obtained by the experiment was calculated as the following Equation 1 with relative comparison percentage. The results obtained at this time are as shown in Table 5 below.

division Example Comparative example One 2 3 One 2 3 Release force (g _f / mm) 13 12 12 34 33 31 Residual Adhesion Rate (%) 97 98 98 65 64 69

As described above, the silicone composition of the present invention eliminated the transfer phenomenon that penetrates the plastic film, which is a representative disadvantage of the solvent type, and the non-solvent type does not adhere to the plastic film and has a high viscosity when coating compared to the solvent type, resulting in nonuniform and precise precision. The disadvantages that could not be compensated for.

In particular, it was designed as a solvent-free type to cope with various environmental regulations and ISO 14000, including VOC regulations, and to provide a silicone cured coating film with a low reduction of residual adhesion rate and excellent air exposure. Has excellent performance.

Although described above with reference to a preferred embodiment of the present invention, those skilled in the art will be variously modified and changed within the scope of the invention without departing from the spirit and scope of the invention described in the claims below I can understand that you can.

1 shows IR data of Pt {P (C ₆ H ₅ ) ₃ } ₂ (C ₂ H ₄ ), which is a platinum catalyst used in the present invention.

Claims (4)

3 to 5% by weight of silicone resin, 70-85 wt% of silicone oil, 3-10 wt% of fumed silica, and Silicone dispersion releasing agent composition, characterized in that the platinum catalyst is contained in 1 to 5% by weight. The silicone dispersion releasing agent composition according to claim 1, wherein the silicone resin has a Q unit: M unit of 1: 0.5 to 1.3 molar ratio represented by the following Chemical Formula 1, and has a number average molecular weight of 1,000 to 10,000. [Formula 1] The silicone dispersion releasing agent composition according to claim 1, wherein the silicone oil is a mixture of vinyl group and hydrogen group in vinyl polysiloxane and hydrogen polysiloxane in a 1: 1.5 to 3.0 molar ratio. The method of claim 1, wherein the platinum catalyst is Pt {P (C ₆ H ₅ ) ₃ } ₂ (C ₂ H ₄ ) alone or Pt {P (C ₆ H ₅ ) ₃ } ₂ (C ₂ H ₄ ) and Pt {P (OC ₆ H ₅ ) ₃ } ₄ , Pt {P (C ₆ H ₅ ) ₃ } ₄ , Pt {P (CH ₃ ) ₃ } ₄ , Pt {P (C ₄ H ₉ ) ₃ } ₄ , Pt {P (OCH ₃ ) ₃ } ₄ , Pt {P (OC ₆ H ₅ ) ₃ } ₄ , Pt {P (C ₆ H ₅ ) ₃ } ₃ , Pt {P (C ₆ H ₅ ) ₃ } ₂ (C ₂ H ₄ ) _, Pt {P (OC ₆ H ₅ ) (OC ₂ H ₅ ) ₂ } ₄ , Pt {P (C ₆ H ₅ ) ₂ (OC ₂ H ₅ )} ₄ and Pt {P (CH ₃ ) ₂ (OC ₄ H ₉ )} ₄ or more of the silicone dispersion releasing agent composition, characterized in that for mixing.