JP2024029704A - Resin composition and laminate - Google Patents

Abstract

The present invention provides a resin composition with low peeling force and antistatic ability, and a method for producing the same. [Solution] A resin composition containing a silicone resin and an onium salt represented by formula (1). Formula (1): Q+・(R1SO2)2N-(1) (In the formula, Q+ represents a pyridinium cation or an imidazolium cation.) R1 in formula (1) is a perfluoroalkyl group with a carbon chain of 1 or a fluorocarbon group. represents a group. [Selection diagram] None

Description

The present invention relates to an onium salt-containing resin composition having a silyl group and a laminate thereof.

There is a known report on imparting antistatic function to a resin composition using a conductive polymer (PEDOT dispersion) (Patent Document 1).

JP2020-23690A

It has been found that resin compositions containing conductive polymers and silicone resins have a problem in that their peeling force increases due to coloring or an increase in adhesive area.
Therefore, the present invention provides a resin composition containing a silicone resin that has low peeling force and is endowed with antistatic ability.

As a result of extensive research, the present inventors have found that by incorporating a certain amount of onium salt having a silyl group in the cationic moiety into a silicone resin, the silicone resin is imparted with antistatic ability without impairing release properties. It was discovered that a resin composition can be obtained, and the present invention was completed.

The present invention is as follows.

［２］一般式（２）（３）中のＲ_３が、炭素数２のアルキル基である［１］に記載のオニウム塩を含む樹脂組成物。
［３］一般式（１）中のＲ_１が、炭素鎖がフルオロ基である［１］又は［２］に記載のオニウム塩を含む樹脂組成物。
［４］シリコーン系樹脂１００質量部に対して、式（１）で表されるオニウム塩を０．１～１０質量部含むことを特徴とする［１］～［３］のいずれかに記載の樹脂組成物。
［５］前記シリコーン系樹脂が付加反応型シリコーン系樹脂である［１］～［４］のいずれかに記載の樹脂組成物。
［６］［１］～［３］のいずれかに記載のオニウム塩を含む離型剤。
［７］［１］～［３］のいずれかに記載のオニウム塩を含む離型層。
［８］［７］に記載の離型層が、基材上に形成された積層体。
［９］プライマー層を有しない［８］に記載の積層体。
［１０］積層体の表面抵抗率が１．０×１０^１２（Ω／□)以下である［７］又は［８］に記載の積層体。
［１１］基材上に、［１］～［５］のいずれかに記載の樹脂組成物を含有する離型剤を塗布し、加熱硬化させて離型層を形成させる工程を含む積層体の製造方法。 [1] A resin composition containing a silicone resin and an onium salt represented by formula (1).
Formula (1): Q ⁺・(R ₁ SO ₂ ) ₂ N ⁻ (1)
(In the formula, Q ⁺ is formula (2) or formula (3))
In formula (1), R ₁ represents a perfluoroalkyl group or a fluoro group having a carbon chain of 1, and in formula (2), R ₂ is the same or different and represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom. It is. In formulas (2) and (3), R ₃ represents an alkyl group having 1 to 3 carbon atoms, and R ₄ represents an alkyl group having 1 to 4 carbon atoms. n represents 1 to 2.

[2] The resin composition containing the onium salt according to [1], wherein R ₃ in general formulas (2) and (3) is an alkyl group having 2 carbon atoms.
[3] A resin composition containing the onium salt according to [1] or [2], wherein R ₁ in general formula (1) is a fluoro group in the carbon chain.
[4] The silicone resin according to any one of [1] to [3], which contains 0.1 to 10 parts by mass of an onium salt represented by formula (1) based on 100 parts by mass of the silicone resin. Resin composition.
[5] The resin composition according to any one of [1] to [4], wherein the silicone resin is an addition reaction type silicone resin.
[6] A mold release agent containing the onium salt according to any one of [1] to [3].
[7] A release layer containing the onium salt according to any one of [1] to [3].
[8] A laminate in which the release layer according to [7] is formed on a base material.
[9] The laminate according to [8], which does not have a primer layer.
[10] The laminate according to [7] or [8], wherein the laminate has a surface resistivity of 1.0×10 ¹² (Ω/□) or less.
[11] A laminate comprising the step of applying a mold release agent containing the resin composition according to any one of [1] to [5] on a base material and curing it by heating to form a mold release layer. Production method.

According to the present invention, it is possible to provide a resin composition containing a silicone resin with low peeling force and imparted with antistatic ability.

The present invention will be explained below.

[Onium salt containing silyl group]
The resin composition of the present invention contains an onium salt represented by formula (1).
Formula (1):
Q ⁺・(R ₁ SO ₂ ) ₂ N ⁻ (1)
(In the formula, Q ⁺ is formula (2) or formula (3))

R ₁ in formula (1) is a perfluoroalkyl group or a fluoro group having 1 to 3 carbon chains, such as a fluoro group, a trifluoromethyl group, a pentafluoroethyl group, or a heptafluoropropyl group, preferably is a fluoro group.

In formulas (2) and (3), R ₂ is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom. This alkyl group may be either linear or branched, preferably a linear alkyl group or a hydrogen atom. Specific examples include methyl group, ethyl group, propyl group, butyl group, etc., and linear alkyl groups having 1 to 2 carbon atoms or hydrogen atoms are particularly preferred. R ₃ is an alkyl group having 1 to 3 carbon atoms, preferably a linear alkyl group. Specific examples of the alkyl group include methyl, ethyl, and propyl groups, with ethyl being preferred. R ₄ is an alkyl group having 1 to 4 carbon atoms. This alkyl group may be either linear or branched, preferably a linear alkyl group. Specific examples include methyl group, ethyl group, propyl group, butyl group, etc., with methyl group being preferred. n in formula (2) and formula (3) represents 1 to 2, preferably 2.

The onium salt (1) of the present invention can be produced by various methods. A typical method is to synthesize an onium halide by reacting an amine with an alkyl halide having a silyl group, and then synthesize an onium salt through a metathesis reaction with an alkali metal imidate salt.

Examples of amines suitable for this synthesis include 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 3-ethylpyridine, 4-ethylpyridine, 2-propylpyridine, and 3-propylpyridine. , 4-propylpyridine, 2-butylpyridine, 3-butylpyridine, 4-butylpyridine, 2,3-dimethylpyridine, 3,4-dimethylpyridine, 1-methylimidazole, 1-ethylimidazole, 1-propylimidazole, Examples include 1-butylimidazole.

Examples of the alkyl halides include chloromethyltrimethoxysilane, 2-chloroethyltrimethoxylane, 3-chloropropyltrimethoxysilane, 4-chlorobutyltrimethoxylane, chloromethyltriethoxysilane, and 2-chloroethyltriethoxysilane. Ran, 3-chloropropyltriethoxysilane, 4-chlorobutyltriethoxylane, chloromethyltripropoxysilane, 2-chloroethyltripropoxylane, 3-chloropropyltripropoxysilane, 4-chlorobutyltripropoxylane, chloromethyl Tributoxysilane, 2-chloroethyltributoxylane, 3-chloropropyltributoxysilane, 4-chlorobutyltributoxylane, bromomethyltrimethoxysilane, 2-bromoethyltrimethoxylane, 3-bromopropyltrimethoxysilane, 4-bromobutyltrimethoxylane, bromomethyltriethoxysilane, 2-bromoethyltriethoxylane, 3-bromopropyltriethoxysilane, 4-bromobutyltriethoxylane, bromomethyltripropoxysilane, 2-bromoethyltripropoxy Ran, 3-bromopropyltripropoxysilane, 4-bromobutyltripropoxylane, bromomethyltributoxysilane, 2-bromoethyltributoxylane, 3-bromopropyltributoxysilane, 4-bromobutyltributoxylane, io- Domethyltrimethoxysilane, 2-iodoethyltrimethoxylane, 3-iodopropyltrimethoxysilane, 4-iodobutyltrimethoxylane, iodomethyltriethoxysilane, 2-iodoethyl Triethoxylane, 3-iodopropyltriethoxysilane, 4-iodobutyltriethoxylane, iodomethyltripropoxysilane, 2-iodoethyltripropoxylane, 3-iodopropyltripolo Poxysilane, 4-iodobutyltripropoxylane, iodomethyltributoxysilane, 2-iodoethyltributoxylane, 3-iodopropyltributoxysilane, 4-iodobutyltributoxylane etc.

The quaternization reaction between amines and alkyl halides may or may not be carried out using a solvent. When a solvent is used, examples of the solvent include alcohols such as methanol, ethanol, and 2-propanol, acetonitrile, ethyl acetate, tetrahydrofuran, and dimethylformamide.

The amount of alkyl halides used may be 0.7 mol or more, preferably 0.9 to 1.5 mol, per 1 mol of amines.

Imidic acid alkali metal salts include bis(trifluoromethanesulfonyl)imide lithium, bis(trifluoromethanesulfonyl)imide sodium, bis(trifluoromethanesulfonyl)imide potassium, bis(fluoromethanesulfonyl)imide lithium, and bis(fluoromethanesulfonyl)imide. Examples include sodium imide, potassium bis(fluoromethanesulfonyl)imide, and the like.

The amount of alkali metal imide salt used in the metathesis reaction is usually 0.8 mol or more, preferably 0.9 mol to 1.2 mol, more preferably 1 to 1 mol, per 1 mol of onium halide. It is .05 mole.

Ion exchange reactions are usually carried out in a solvent. Examples of the solvent include ketones such as acetone and methyl ethyl ketone, alcohols such as methanol, ethanol, and 2-propanol, acetonitrile, ethyl acetate, tetrahydrofuran, and dimethylformamide.

The order of mixing onium halides, alkali metal imidate and the solvent is not particularly limited, and the alkali metal imidate may be added after mixing the onium halides and the solvent, or the alkali metal salt imidate and the alkali metal imidate may be added after mixing the onium halides and the solvent. Onium halides may be added after mixing the solvents.

The reaction temperature in the ion exchange reaction is usually 10°C or higher, preferably 10 to 60°C, particularly preferably 10 to 30°C.

To separate the onium salt from the reaction solution after the reaction is completed, the solvent and the generated inorganic salt are removed from the reaction solution. If an inorganic salt is precipitated in the resulting reaction solution, the reaction solution is filtered to remove the precipitated inorganic salt, and then the onium salt is isolated by appropriately combining unit operations such as concentration, filtration, and extraction. .

The cations represented by formulas (2) and (3) do not poison the platinum catalyst, so they do not inhibit the curing of the silicone mold release agent, and do not reduce solvent resistance due to poor curing. Elution of the release layer to the adherent (adhesive layer, etc.) is suppressed.
Further, since the onium salt represented by formula (1) has excellent compatibility with silicone resin, bleeding out onto the surface is suppressed, and the problem of contaminating the adherend is less likely to occur.
It is known that amine compounds and ammonium cations can poison platinum catalysts. Therefore, ammonium-based onium salts tend to inhibit the curing of the silicone mold release agent, and the release layer elutes to the adherend (adhesive layer, etc.) due to a decrease in solvent resistance due to poor curing. Furthermore, since ammonium-based onium salts have poor compatibility with silicone-based resins, they bleed out onto the surface and cause a problem of contaminating the adherend.

[Resin composition]
The resin composition of the present invention contains a silicone resin, a mixed or copolymer resin of organic and silicone resins, and preferably contains a curable silicone resin in view of its excellent mold release properties and heat resistance.

Curable silicone resins include "addition reaction type" in which organohydrogenpolysiloxane and organopolysiloxane containing alkenyl groups are heated and cured under a platinum catalyst, and organohydrogenpolysiloxane and organopolysiloxane containing alkenyl groups are heat-cured. "Condensation polymerization reaction type" is produced by heat-curing organopolysiloxane containing alkenyl group and organopolysiloxane containing mercapto group using a photopolymerization catalyst. There are ``radical addition type'' which cures, and ``cationic polymerization type'' which cures by photo-ring-opening the epoxy group with an onium salt initiator. An addition reaction type in which siloxane and an organopolysiloxane containing an alkenyl group are cured by heating under a platinum catalyst, or a cationic polymerization type or organopolysiloxane in which the epoxy group is photo-ring-opened with an onium salt initiator to cure it. A radical addition type of curing using a photopolymerization catalyst is preferable.
The resin composition in the present invention can be formed by curing the coating composition after removing the solvent in a drying step if necessary.

[Coating composition]
The aforementioned coating composition is a mixture that exhibits liquid properties at room temperature, and includes a material capable of forming a resin composition, a polymerization initiator, a curing agent, a curing catalyst, and further contains a solvent, particles, an antistatic agent, etc. It may also contain various additives.
The composition of the coating composition is not particularly limited, but as mentioned above, from the viewpoint of mold release properties and heat resistance, it is preferable to use a resin precursor that can form a silicone resin, especially a curable silicone resin. A coating composition containing a resin precursor of a type, a condensation reaction type, a radical addition type, or a cationic polymerization type, as well as a polymerization initiator, a curing agent, and a curing catalyst is more preferable; , is more preferable.
The coating composition can be used as a mold release agent.

Specific examples of the addition reaction type silicone resin precursor and catalyst include those containing polydimethylsiloxane and hydrogen siloxane containing a vinyl group at the end, such as KS-3650 manufactured by Shin-Etsu Chemical Co., Ltd.; KS843, KS847, KS847H, KS847T, 759, LTC755, LTC761, LTC856 etc. can be mentioned.

Since it is necessary to sufficiently impart antistatic properties while maintaining release properties, the concentration of the onium salt in the resin composition of the present invention is usually 0.1 to 10% by weight based on 100 parts by mass solid content of the silicone resin. It is preferably 1 to 5 parts by weight, and more preferably 1 to 5 parts by weight.

The solid content concentration of the coating composition in the present invention is not particularly limited, but when the coating composition contains a solvent, it is usually 10% by mass or less, and more preferably 0.5 to 5% by mass. It is preferable that there be.

The coating composition of the present invention does not need to be coated in two layers as a support base so that a primer layer having an antistatic layer and a release layer are formed so as not to impair mold release performance. Can be coated.

[Other paint composition additives]
The coating composition may contain a solvent, and preferably contains a solvent from the viewpoint of manufacturing suitability. The term "solvent" as used herein refers to a substance that is liquid at normal temperature and pressure and can be almost completely evaporated in the drying process after coating. Coating compositions suitable for the laminates of the present invention may include a solvent. The number of types of solvents is preferably 1 to 10 types, more preferably 1 to 5 types, and still more preferably 1 to 3 types. A release layer can be formed by drying the coating composition.

Solvents include aromatic hydrocarbons such as toluene, aliphatic hydrocarbons such as hexane, ketones such as ethyl methyl ketone (MEK) and isobutyl methyl ketone, esters such as ethyl acetate and butyl acetate, ethanol, 2- Alcohols such as propanol, ethers such as diisopropyl ether, dibutyl ether, etc. can be used. Considering solubility, coatability, boiling point, etc., these are preferably used alone or in combination.

Since an aqueous solvent can poison the platinum catalyst necessary for curing the silicone mold release agent, it is preferable to use an organic solvent as the solvent for the coating composition in the present invention.

[Supporting base material]
Examples of the supporting base material in the present invention include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, polyethylene films, polypropylene films, polyvinyl chloride films, polyvinylidene chloride films, polyvinyl alcohol films, and ethylene-vinyl acetate. Copolymer film, polystyrene film, polycarbonate film, polymethylpentene film, polysulfone film, polyetheretherketone film, polyethersulfone film, polyphenylene sulfide film, polyetherimide film, polyimide film, fluororesin film, polyamide film, acrylic Examples include resin films, norbornene resin films, cycloolefin resin films, etc., and polyethylene terephthalate films are particularly preferred as supporting base materials that are suitably used when used as release films.

[Method for producing release film using addition-curing silicone precursor]
The method of applying the coating composition onto the supporting substrate is not particularly limited, but a layer can be formed by applying the coating composition onto the supporting substrate by dip coating, roller coating, wire bar coating, gravure coating, etc. It is preferable to form Furthermore, among these coating methods, the wire bar coating method is more preferable. Next, the liquid film applied onto the support base material or the like is dried. In addition to completely removing the solvent from the resulting laminate, the drying step preferably involves heating the liquid film, from the viewpoint of accelerating the curing of the coating film. In the drying step, when curing with heat, the temperature is preferably from room temperature to 200°C or less, more preferably from 80°C to 200°C, and even more preferably from 80°C to 150°C, from the viewpoint of activation energy of the curing reaction. below ℃.

[Contact angle]
The contact angle of water on the surface of the produced release film on which the release layer was formed was determined by the θ/2 method using a contact angle meter CAX150 manufactured by Kyowa Interface Science Co., Ltd. as a measurement device at a temperature of 25°C and a humidity of 50%. Under these conditions, 1 μL of pure water is dropped onto the surface of the release layer, and the contact angle can be measured 1 second after dropping.

When the contact angle is large, the peeling force when peeling off the adherend is reduced, and it can be suitably used as a release film. The resin composition of the present invention has excellent compatibility between the onium salt and the silicone resin, and bleed-out of the onium salt to the surface is suppressed, so that it is possible to increase the peeling force of the release layer. However, it is possible to impart antistatic performance. The contact angle is preferably 95° or more, more preferably 100° or more, and even more preferably 104° or more.

[Surface resistivity]
The surface resistivity of the resin composition can be measured at room temperature, 50% RH, and an applied voltage of 100 V using Hirester UP (MCP-HT450).

When the thickness of the resin composition is 0.5 μm, the surface resistivity is preferably 1.0×10 ¹² (Ω/□) or less, and 1.0×10 ¹¹ (Ω/□) or less. is more preferable, and more preferably 8.0×10 ¹⁰ (Ω/□) or less.

[Application]
Furthermore, the resin composition of the present invention can be particularly suitably used as a release film for the adhesive layer of a protective film.

Next, the present invention will be explained based on Examples, but the present invention is not necessarily limited to these. In addition, regarding the same compound, the same product was used unless otherwise specified.

(Synthesis example 1)
A mixture of 9.3 g (100 mmol) of 3-methylpyridine and 25.2 g (105 mmol) of 3-chloropropyltriethoxysilane was stirred at 110° C. for 48 hours to react. After the reaction was completed, the mixture was dried under reduced pressure to obtain 30.0 g (yield: 90%) of 1-(triethoxysilylpropyl)-3-methylpyridinium chloride.
30.0 g (90 mmol) of the obtained 1-(triethoxysilylpropyl)-3-methylpyridinium chloride was dissolved in 30 g of ethanol, and 25.8 g (90 mmol) of lithium bis(trifluoromethanesulfonyl)imidate was added. After that, the mixture was stirred at room temperature for 1 hour. After filtering the reaction solution, inorganic salts were removed by washing with pure water. After concentration, 48.1 g (yield 95%) of liquid 1-(triethoxysilylpropyl)-3-methylpyridinium bis(trifluoromethanesulfonyl)imide was obtained.

(Synthesis example 2)
Liquid 1-(triethoxysilylpropyl)-3-methyl was synthesized under the same conditions as in Synthesis Example 1 except that lithium bis(fluorosulfonyl)imidate was used instead of lithium bis(trifluoromethanesulfonyl)imidate. 38.8 g (yield 93%) of pyridinium bis(fluorosulfonyl)imide was obtained.

(Synthesis example 3)
A mixture of 8.21 g (100 mmol) of 1-methylimidazolium and 25.2 g (105 mmol) of 3-chloropropyltriethoxysilane was reacted by stirring at 110° C. for 48 hours. After the reaction was completed, the mixture was dried under reduced pressure to obtain 30.6 g (yield: 95%) of 1-methyl-3-(triethoxysilylpropyl)imidazolium chloride.
30.6 g (95 mmol) of the obtained 1-methyl-3-(triethoxysilylpropyl) imidazolium chloride was dissolved in 30 g of ethanol, and 27.2 g (95 mmol) of lithium bis(trifluoromethanesulfonyl)imidate was dissolved therein. After the addition, the mixture was stirred at room temperature for 1 hour. After filtering the reaction solution, inorganic salts were removed by washing with pure water. After concentration, 52.8 g (yield 98%) of liquid 1-methyl-3-(triethoxysilylpropyl)imidazolium bis(trifluoromethanesulfonyl)imide was obtained.

(Synthesis example 4)
Liquid 1-methyl-3-(triethoxysilylpropyl) was synthesized under the same conditions as in Synthesis Example 1 except that lithium bis(fluorosulfonyl)imidate was used instead of lithium bis(trifluoromethanesulfonyl)imidate. 41.7 g (yield 94%) of imidazolium bis(fluorosulfonyl)imide was obtained.

(Synthesis example 5)
A mixture of 8.21 g (100 mmol) of 3-methylpyridine and 20.8 g (105 mmol) of 3-chloropropyltrimethoxysilane was reacted by stirring at 110° C. for 24 hours. After the reaction was completed, the mixture was dried under reduced pressure to obtain 27.7 g (yield: 95%) of 1-(trimethoxysilylpropyl)-3-methylpyridinium chloride.
27.7 g (95 mmol) of the obtained 1-(trimethoxysilylpropyl)-3-methylpyridinium chloride was dissolved in 30 g of ethanol, and 27.2 g (95 mmol) of lithium bis(trifluoromethanesulfonyl)imidate was added. After that, the mixture was stirred at room temperature for 1 hour. After filtering the reaction solution, inorganic salts were removed by washing with pure water. After concentration, 40.7 g (yield: 80%) of liquid 1-(trimethoxysilylpropyl)-3-methylpyridinium bis(trifluoromethanesulfonyl)imide was obtained.

(Synthesis example 6)
Liquid 1-(trimethoxysilylpropyl)-3-methyl was synthesized under the same synthesis conditions as in Synthesis Example 5 except that lithium bis(fluorosulfonyl)imidate was used instead of lithium bis(trifluoromethanesulfonyl)imidate. 34.4 g (yield: 83%) of pyridinium bis(fluorosulfonyl)imide was obtained.

(Synthesis example 7)
A mixture of 8.21 g (100 mmol) of 1-methylimidazole and 20.8 g (105 mmol) of 3-chloropropyltrimethoxysilane was reacted by stirring at 110° C. for 24 hours. After the reaction was completed, the mixture was dried under reduced pressure to obtain 26.9 g (yield: 96%) of 1-methyl-3-(trimethoxysilylpropyl)imidazolium chloride.
26.9 g (96 mmol) of the obtained 1-methyl-3-(trimethoxysilylpropyl) imidazolium chloride was dissolved in 30 g of ethanol, and 27.4 g (96 mmol) of lithium bis(trifluoromethanesulfonyl)imidate was dissolved. After the addition, the mixture was stirred at room temperature for 1 hour. After filtering the reaction solution, inorganic salts were removed by washing with pure water. After concentration, 42.8 g (yield: 85%) of liquid 1-methyl-3-(trimethoxysilylpropyl)imidazolium bis(trifluorosulfonyl)imide was obtained.

(Synthesis example 8)
Liquid 1-methyl-3-(trimethoxysilylpropyl) was synthesized under the same conditions as in Synthesis Example 7 except that lithium bis(fluorosulfonyl)imidate was used instead of lithium bis(trifluoromethanesulfonyl)imidate. 34.7 g (yield: 85%) of imidazolium bis(fluorosulfonyl)imide was obtained.

A coating composition was prepared by mixing the following materials and applied to a film to obtain a release film.

(Example 1)
[Preparation of paint composition]
・Methyl vinyl polysiloxane and methyl hydrogenated polysiloxane (silicone resin precursor solid content): 100 parts by mass
(KS847 manufactured by Shin-Etsu Chemical Co., Ltd. Solid content concentration 30% by mass)
・Methylvinylpolysiloxane and platinum complex solution: 3 parts by mass (CAT_PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.)
Onium salt of Synthesis Example 1: 2 parts by mass The above composition was diluted with toluene:MEK=7:1 to prepare a paint having a solid content concentration of 5% by mass.

[Coating conditions]
The paint was coated on a PET film using a bar coater to a thickness of about 500 nm after drying, and heated at 100° C. for 1 minute to prepare a test piece.

(Example 2)
A paint was prepared without any changes except that Synthesis Example 2 was used with the onium salt of Example 1, and the paint was applied to a PET film to prepare a test piece.

(Example 3)
A coating material was prepared without any changes except that the onium salt of Example 1 was used in Synthesis Example 3, and it was applied to a PET film to prepare a test piece.

(Example 4)
A paint was prepared without any changes except that Synthesis Example 4 was used with the onium salt of Example 1, and it was applied to a PET film to prepare a test piece.

(Example 5)
A paint was prepared without any changes except that Synthesis Example 5 was used with the onium salt of Example 1, and it was applied to a PET film to prepare a test piece.

(Example 6)
A paint was prepared without any changes except that Synthesis Example 6 was used with the onium salt of Example 1, and it was applied to a PET film to prepare a test piece.

(Example 7)
A paint was prepared without any changes except that Synthesis Example 7 was used for the onium salt of Example 1, and it was applied to a PET film to prepare a test piece.

(Example 8)
A paint was prepared without any changes except that Synthesis Example 8 was used with the onium salt of Example 1, and it was applied to a PET film to prepare a test piece.

(Comparative example 1)
A coating material was prepared without changing the onium salt of Example 1 except that 1-octylpyridinium bis(fluorosulfonyl)imide was used, and it was applied to a PET film to prepare a test piece.

(Comparative example 2)
A coating material was prepared without changing the onium salt of Example 1 except that 1-butyl-3-methylimidazolium bis(fluorosulfonyl)imide was used, and it was applied to a PET film to prepare a test piece.

(Comparative example 3)
A coating material was prepared without changing the onium salt of Example 1 except that trimethyldodecyl ammonium bis(fluorosulfonyl)imide was used, and it was applied to a PET film to prepare a test piece.

(Comparative example 4)
A paint was prepared without changing the conditions of Example 1 except that no onium salt was added, and it was applied to a PET film to prepare a test piece.

[Surface resistivity measurement]
The surface resistivity of the coated surface of the test piece was measured using Hirester UP (MCP-HT450) at room temperature, 50% RH, and an applied voltage of 100 V.

[Peeling test]
Nitto Denko No. 1 for silicone mold release coated surfaces. No. 31 tape was applied, and after curing for 1 hour, the peel force at 180° peeling was measured at a peel speed of 0.3 m/min.

[Contact angle]
The contact angle of water on the surface of the produced release film on which the release layer was formed was determined by the θ/2 method using a contact angle meter CAX150 manufactured by Kyowa Interface Science Co., Ltd. as a measurement device at a temperature of 25°C and a humidity of 50%. Under these conditions, 1 μL of pure water was dropped onto the surface of the release layer, and the contact angle was measured 1 second after dropping.

[Solvent resistance]
After rubbing the laminate 10 times with a cotton cloth impregnated with toluene and drying the solvent adhering to the laminate, the degree of layer shedding was visually determined according to the following criteria.
○: No falling off.
×: Falling off.

The results of Examples 1 to 8 and Comparative Examples 1 to 4 are shown in Table 1.

As mentioned above, the resin compositions of Examples 1 to 8 of the present invention have low surface resistivity, antistatic performance required for peeling antistatic properties, reduced peeling force, and contact The large corners prevented contamination of the adherend due to bleed-out of the onium salt, and no decrease in solvent resistance due to poor curing was observed.

The resin composition of the present invention has antistatic ability and has low peeling force, so it can be used as a mold release agent and a mold release layer.

Claims (11)

A resin composition containing a silicone resin and an onium salt represented by formula (1).
Formula (1): Q ⁺・(R ₁ SO ₂ ) ₂ N ⁻ (1)
(In the formula, Q ⁺ is formula (2) or formula (3))
In formula (1), R ₁ represents a perfluoroalkyl group or a fluoro group having a carbon chain of 1, and in formula (2), R ₂ is the same or different and represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom. It is. In formulas (2) and (3), R ₃ represents an alkyl group having 1 to 3 carbon atoms, and R ₄ represents an alkyl group having 1 to 4 carbon atoms. n represents 1 to 2.

The resin composition containing an onium salt according to claim 1, wherein R ₃ in general formulas (2) and (3) is an alkyl group having 2 carbon atoms. The resin composition containing an onium salt according to claim 1 or 2, wherein R ₁ in general formula (1) is a fluoro group. The resin composition according to claim 3, comprising 0.1 to 10 parts by mass of an onium salt represented by formula (1) based on 100 parts by mass of the silicone resin. The resin composition according to claim 1 or 2, wherein the silicone resin is an addition reaction type silicone resin. A mold release agent comprising the onium salt according to claim 1 or 2. A release layer comprising the onium salt according to claim 1 or 2. A laminate in which the release layer according to claim 7 is formed on a base material. The laminate according to claim 8, which does not contain a primer layer. The laminate according to claim 8, wherein the laminate has a surface resistivity of 1.0×10 ¹² (Ω/□) or less. A method for producing a laminate, comprising a step of applying a mold release agent containing the resin composition according to claim 1 or 2 onto a base material, and heating and curing the mold release agent to form a mold release layer.