JP2004091777A - Release agent and release film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a silicon-free release agent which is free from silicone, exhibits a good release characteristic against various pressure-sensitive adhesives, does not transfer to an adhesive surface and is excellent in heat resistance, solvent resistance, rubbing-off performance (scratch resistance) and transfer coating performance. <P>SOLUTION: The release agent contains (A) a polyolefin elastomer having an epoxy group and may contain (B) a reactive compound having a functional group reactive with an epoxy group. <P>COPYRIGHT: (C)2004,JPO

Description

The present invention relates to a release film containing no silicone, having a small peeling force, having excellent heat resistance and solvent resistance, and a release film having a release layer formed by curing the release agent on a support. .

Adhesive sheets are used in many fields because they can be adhered to the adherend simply by light pressure bonding. These are usually provided with a release layer on the back of a support having an adhesive layer on one side to facilitate rewinding and the like during use. In the case of double-sided adhesive sheets and the like, a release film having a release layer on a support is used to facilitate protection of the adhesive surface and rewinding during use.

The release layer of the pressure-sensitive adhesive sheet or release film subjected to such back surface release treatment is mainly classified into silicone-based, long-chain alkyl-based, and wax-based. Is used properly. Of these, long-chain alkyl release agents do not scatter silicone components due to heating, have relatively high degree of freedom in synthesis, such as introduction of polar groups, and can adjust the surface properties of polymers. There is an advantage that ink printability can be imparted. For this reason, they are widely used for binding tapes, gum tapes, and tapes for electronic materials that dislike silicone components, but have a problem in peeling strength after immersion in a solvent.

Silicone-based release agents contain silicone-based gas generating components, require the use of special catalysts and heat treatment, and have the disadvantages of being able to achieve release properties only by drying after application and short pot life. There is. In particular, when used in the molding process of electronic equipment-related parts, there is a problem that the product yield is reduced due to contamination by silicone, and a release agent containing no silicone is required.

In order to solve such problems, non-silicone release agents include polyvinyl carbamate (reacted product of polyvinyl alcohol and C ₁₈ H ₃₇ NCO), which is a polymer having a long chain alkyl group, and polyethyleneimine and C ₁₈ H ₃₇ NCO. It has been proposed to use a reactant of However, when these release agents are used in some applications such as green sheets, "repelling" occurs, and peeling cannot be performed with a peeling force as low as that of silicone, resulting in problems such as poor solvent resistance.

と し て As a release agent suitable for the above-mentioned applications, a release agent whose surface energy is reduced by a halogen compound such as fluoride has been proposed. For example, JP-A-55-165925, JP-A-1-198349, JP-A-4-246532, JP-A-4-270649, JP-A-4-290746, JP-A-2000-263714, and JP-A-2001-129940. And release agents described in JP-A-2001-138338. However, most of these release agents require a larger peeling force than current silicone-based release agents. Further, dehalogenation has recently been required to reduce the environmental burden in waste treatment, but these release agents do not always follow the trend of such an era.

JP-A-2001-131505 proposes a release film formed by coating a copolymer containing perfluoroalkylvinyl as a main component. This release film exhibits excellent release properties, but its use is greatly restricted because the copolymer is insoluble in general organic solvents and only soluble in special and expensive solvents such as FR thinners.

Furthermore, Japanese Patent Application Laid-Open No. 2001-138338 describes a release film formed by laminating a fluororesin on a resin film. However, there is a problem in that the thickness of the release layer exceeds a few μm, and the production cost and the surface roughness are inferior to those of the silicone release film.
In addition, polyolefin rubber is also known to act as a release layer, but because of the problem of solvent resistance, it is difficult to transfer and apply an adhesive, and depending on the base material, adhesion is poor, and Since it is soft and has no surface strength, there is a problem that it is easily damaged.
JP-A-55-165925 JP-A-1-198349 JP-A-4-246532 JP-A-4-270649 JP-A-4-290746 JP 2000-263714 A JP 2001-129940 A JP 2001-138338 A JP 2001-131505 A

Thus, conventionally known release agents and release films are not always satisfactory. In view of the above circumstances, the present invention does not contain silicone, shows good release properties to various pressure-sensitive adhesives, does not migrate to the pressure-sensitive adhesive surface, and has heat resistance, solvent resistance, rub-off property (scratch resistance). ), To provide a non-silicone release agent and a release film having excellent transfer coatability.

As a result of intensive studies, the present inventors have found that using a polyolefin elastomer and a composition containing a compound compatible with and crosslinked with the polyolefin elastomer can provide an excellent release agent that solves the above-mentioned problems. Reached the present invention.

That is, the present invention provides a release agent containing a polyolefin elastomer (A) having an epoxy group. The release agent of the present invention may contain a reactive compound (B) having a functional group capable of reacting with an epoxy group. Examples of the functional group capable of reacting with the epoxy group include a hydroxyl group, an amino group, a carboxyl group, an epoxy group, and an acid anhydride group. Preferred examples of the reactive compound (B) include a hydroxyl group and an amino group. And a polyolefin having a carboxyl group or an epoxy group. The release agent of the present invention contains, together with the polyolefin elastomer (A) having an epoxy group, a polymerization catalyst for subjecting the epoxy group of the polyolefin elastomer (A) to ring-opening polymerization in the presence of heat and / or active energy rays. May be.

The present invention provides a step of applying a release agent to at least one surface of a base film to form a release agent-containing layer, and heating the release agent-containing layer to react the polyolefin elastomer (A) with the reactive compound. The present invention also provides a method for producing a release film having a release layer on at least one side, comprising a step of reacting (B) and / or subjecting the epoxy group of the polyolefin elastomer (A) to ring-opening polymerization.
The present invention also provides a release film having a release layer obtained by curing the above-mentioned release agent on at least one surface of a substrate film made of a thermoplastic polyester film or the like, and the above-mentioned release film on at least one surface of paper. A release paper having a release layer obtained by curing an agent is also provided.

The release agent of the present invention does not contain contaminating silicone, has no problems in workability such as coating, is excellent in solvent resistance, heat resistance, scratch resistance, transfer coating property, and releases to an adhesive surface. It has excellent mold performance and sufficiently satisfies the original required characteristics as a release agent.

離 The release film of the present invention is preferably used in a semiconductor manufacturing process or a ceramic green sheet manufacturing process. Further, the release film of the present invention can be preferably used as an adhesive tape or a surface protective film. Further, a container can be manufactured using the release film of the present invention.

Embodiment of the Invention

(4) Hereinafter, the release agent and the release film of the present invention will be described in detail. In this specification, “to” is used to mean that the numerical values described before and after it are included as the lower limit and the upper limit. In this specification, “(meth) acrylate” is used to mean both acrylate and methacrylate.

As the polyolefin elastomer (A) having an epoxy group (hereinafter sometimes abbreviated as “epoxidized polyolefin elastomer (A)”) used in the release agent of the present invention, an olefin monomer is homopolymerized, or two types thereof are used. A polymer obtained by reacting a compound obtained by copolymerizing the above-mentioned olefin monomer with a compound having an epoxy group, or a copolymer obtained by copolymerizing a reactive monomer having an epoxy group with olefin as a main component can be used widely.

具体 Specific examples of the polyolefin elastomer raw material used for the modification include homopolymers and copolymers of α-olefins such as ethylene, propylene, butene, hexene, and octene. Further, a copolymer of ethylidene norbornene, norbornene, and the like and an α-olefin such as ethylene is also included. Further, a hydrocarbon-based elastomer such as a diene rubber obtained by living polymerization represented by polyisoprene, a polymer obtained by hydrogenating them, and an elastomer obtained by ring-opening polymerization of a cyclic olefin can also be used. . Examples of the olefin polymer obtained by ring-opening polymerization of a cyclic olefin include ring-opening polymers of alicyclic olefins such as cyclopentene, cyclooctene, and norbornene. Furthermore, polyolefins obtained by hydrogenation such as a nuclear hydrogenated product of a styrene / butadiene copolymer and a nuclear hydrogenated product of a styrene isoprene copolymer can also be used.

で は In the present invention, it is preferable to use a polyolefin-based elastomer obtained by polymerization with a metallocene catalyst as the raw material of the polyolefin elastomer. Polymerization using a metallocene catalyst makes it possible to obtain a polyolefin-based elastomer having a narrow molecular weight distribution and a small amount of low molecular weight components. When a metallocene catalyst is used, uniform copolymerization is possible, and the generation of low molecular weight components whose comonomer content is significantly different from the average composition can be suppressed. For this reason, it is possible to suppress stickiness of the obtained coating film, and to uniformly introduce a crosslinking group for imparting chemical resistance to the coating film, and as a result, efficient gelation is possible, A release agent having high chemical resistance, heat resistance, and coating film strength can be obtained.

Specific examples of the metallocene catalyst include rac-isopropylidenebis (1-indenyl) zirconium dichloride, rac-dimethylsilylbis-1- (2-methylindenyl) zirconium dichloride, rac-dimethylsilylbis-1- (2- Methyl-4-phenylindenyl) zirconium dichloride, rac-dimethylsilylbis-1- (2-methyl-4.5-benzoindenyl) zirconium dichloride, isopropylidene-9-fluorenylcyclopentadienyl zirconium dichloride, Dimethylsilylenebis (cyclopentadienyl) zirconium dichloride and the like can be mentioned. In these polymerizations, commonly used co-catalysts, that is, organoaluminums such as triethylaluminum and methylalumoxane, and tetrakis (pentafluorophenyl) borate can be used.

エ ポ キ シ The epoxidized polyolefin elastomer (A) used in the present invention preferably has a melt flow index (MFR) at 180 ° C of 100 g / 10 minutes or less. The MFR has a correlation with the average molecular weight of the olefin-based elastomer, and the higher the MFR, the smaller the average molecular weight. If the MFR exceeds 100 g / 10 minutes, sufficient film strength may not be obtained when a release layer is formed. A preferred MFR is 50 g / 10 minutes or less, and a more preferred MFR is 10 g / 10 minutes or less. When the polyolefin elastomer raw material is modified, the MFR value may decrease or increase due to the modification. Therefore, it is preferable to appropriately select the raw material so as to fall within the above range after the modification.

Next, we describe denaturation. The epoxidized polyolefin elastomer (A) is obtained by copolymerizing a (meth) acrylate monomer having an epoxy group with a monomer for producing a polyolefin, or a radical initiator in a solution, a molten state or a suspension state of the polyolefin elastomer. Or by reacting with a monomer having an epoxy group in the presence of an epoxy group to introduce an epoxy group into the polyolefin chain.

Examples of monomers having an epoxy group include glycidyl (meth) acrylate, 4-hydroxylbutyl (meth) acrylate glycidyl ether, 3,4-epoxycyclohexyl (meth) acrylate, bisphenol A (meth) acrylic acid monoester monoglycidyl ether, and butyl Glycidyl maleate, butyl glycidyl fumarate, propyl glycidyl malate, N- [4- (2,3-epoxypropoxy) -3,5-dimethylbenzyl] acrylamide and the like can be mentioned. In order to further increase the crosslinking rate, a monomer having a long-chain epoxy group may be preferable.

The epoxidized polyolefin elastomer (A) used in the present invention may have a functional group that does not react with the epoxy group to such an extent that the release properties of the release agent of the present invention are not excessively reduced. For example, such functional groups include (meth) acrylate groups, vinyl groups, ether groups, alkyl groups, halogen atoms, ester groups, carbonyl groups, and the like. These may be used alone or in combination of two or more kinds, and a vinyl compound other than those described above, for example, styrene may be used in combination.

The amount of the modifier added at the time of modification for introducing an epoxy group into the polyolefin elastomer is 0.01 to 40 parts by weight, preferably 0.05 to 30 parts by weight, based on 100 parts by weight of the polyolefin elastomer raw material.

Examples of the radical initiator necessary for graft-polymerizing the above-mentioned modifier having an epoxy group to a polyolefin elastomer include t-butyl hydroperoxide, cumyl hydroperoxide, 2,5-dimethylhexyl 2,5-dihydroperoxide. Oxide, t-butylperoxybenzoate, benzoyl peroxide, dicumyl peroxide, 1,3-bis (t-butylperoxyisopropyl) benzene, dibutyl peroxide, methyl ethyl ketone peroxide, potassium peroxide, hydrogen peroxide, etc. Azo such as organic and inorganic peroxides, 2,2'-azobisisobutyronitrile, 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], azodi-t-butane Compounds and carbon radical generators such as dicumyl can be used. These radical polymerization initiators can be appropriately selected in relation to a modifier and reaction conditions, and two or more kinds can be used in combination. Further, the radical polymerization initiator can be used by dissolving it in an organic solvent or the like.
The amount of the radical polymerization initiator used is in the range of 0.01 to 30 parts by weight, preferably 0.05 to 10 parts by weight, based on 100 parts by weight of the polyolefin elastomer raw material.

For the denaturation reaction, a solution denaturation performed in a solution in which at least one of the reaction substrates is dissolved, a suspension denaturation performed in a system in which all of the reaction substrates are not dissolved, or a method based on melt kneading is used. Solution denaturation or melt denaturation performed in a dissolved state is preferred.
The apparatus used for melt kneading is an extruder or a stirrer, specifically, a horizontal twin-screw stirrer such as a Labo Plastomill, a single-screw or twin-screw kneader, a horizontal twin-screw multi-disc device, or a horizontal twin-screw renewer. Or a vertical stirrer such as a double helical ribbon stirrer. The melting and kneading temperature can be set at any temperature as long as the polyolefin elastomer is in a molten state, but is preferably 300 ° C. or lower in order to prevent deterioration of the resin. Melt kneading time is preferably in the range of 0.1 to 10 minutes, more preferably 0.5 to 5 minutes. Melt kneading may be performed under reduced pressure conditions to prevent deterioration and remove ungrafted products. The pressure at this time is 200 mmHg or less, more preferably 100 mmHg or less.

As a method of adding the modifier and the radical polymerization initiator, there is a method of dry-blending with the polyolefin elastomer and kneading all at once, or a method of dry-blending the elastomer with either the modifier or the radical polymerization initiator and adding the other during kneading. And a method of adding a modifier and a radical initiator to a molten elastomer. Further, a small amount of an organic solvent such as xylene may be added to improve the reaction efficiency.

In the present invention, a plurality of types of polyolefin elastomers may be used in combination as the epoxidized polyolefin elastomer (A). Further, an unmodified polyolefin elastomer may be added as an additional component. Examples of the unmodified polyolefin elastomer include those exemplified as raw materials for the epoxidized polyolefin elastomer.

In the present invention, a crystalline polyolefin elastomer can be used for both the epoxidized polyolefin elastomer (A) and the unmodified polyolefin elastomer in order to obtain heat resistance and chemical resistance. The crystallinity of the polyolefin functions as a physical cross-linking point and improves heat resistance, chemical resistance, and film strength. However, polyolefin elastomers having crystallinity impair the preservability of the coating liquid due to crystallization when used as a coating liquid, and the coating film has a high modulus of elasticity when applied to the film surface, resulting in reduced releasability. Tend to be. In order to obtain excellent peeling force and good chemical resistance and heat resistance, it is preferable to adjust the crystallinity of the epoxidized polyolefin elastomer (A) or the unmodified polyolefin elastomer according to required characteristics. As a method of controlling the crystallinity, a method of appropriately controlling the stereoregularity of the olefin polymer to adjust the crystallinity, a method of performing the copolymerization to control the crystallinity and the glass transition temperature, or a blending method. An adjustment method or the like can be used. Further, the crystallinity can be adjusted by changing the monomer composition and the chain length of the polyolefin-based elastomer.

Next, the reactive compound (B) used in the release agent of the present invention will be described.
The type and production method of the reactive compound (B) used in the release agent of the present invention are not particularly limited as long as it has a functional group capable of reacting with an epoxy group. For example, an elastomer having a functional group capable of reacting with an epoxy group can be preferably exemplified. Such an elastomer can be prepared by a method such as copolymerizing a monomer having a reactive functional group during the polymerization of the elastomer or modifying the polyolefin elastomer by adding a compound having a reactive functional group.

種類 The type of the functional group that can react with the epoxy group is not particularly limited, and can be appropriately selected from a wide range of reactive functional groups. Examples include a hydroxyl group, an amino group, a carboxyl group, an epoxy group, and an acid anhydride group.

Specific examples of the reactive compound (B) having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-hydroxyhexyl (meth). Acrylate, 2-, 3- or 4-hydroxycyclohexyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, tetraethylene glycol mono (meth) acrylate, 2- Hydroxyl-3-phenoxypropyl (meth) acrylate, diethylene glycol (meth) acrylate, polyethylene glycol mono (meth) acrylate, N-methylol (meth) acrylamide and other hydroxyl-containing reactive monomers Modified polyolefin with mer, mention may be made of polyhydric alcohol compounds. A compound having a hydroxyl group generates a proton having the highest reactivity as a cation species upon reaction with a cation, so that the reaction rate is greatly increased. When a reactive proton-modified polyolefin is used, a monomer having a long-chain hydroxyl group may be preferable in order to increase the crosslinking rate.

The type of the polyhydric alcohol compound is not particularly limited. For example, various polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide-propylene oxide copolymer, aliphatic polyester polyol, polybutadiene polyol, hydrogenation Polybutadiene polyols, acrylic polyols, aliphatic polycarbonate polyols, polycaprolactone polyols, polymer polyols and the like, as well as polymers having a hydroxyl group-containing monomer such as hydroxyethyl (meth) acrylate-various (meth) acrylate copolymers, A modified polyvinyl alcohol having an appropriate amount of hydroxyl group left can be used. In particular, it is preferable to use hydrogenated polybutadiene polyol and polycaprolactone polyol.

As the reactive compound (B) having an amino group, a compound having a primary amine or a secondary amine is preferable. Specific examples of these include 2-aminoethyl (meth) acrylate, 2- (methylamino) ethyl (meth) acrylate, 2- (ethylamino) ethyl (meth) acrylate, 3-aminopropyl (meth) acrylate, -(Methylamino) propyl (meth) acrylate, 3- (ethylamino) propyl (meth) acrylate, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N- (2-amino A) Polyolefin modified with ethyl (meth) acrylamide, N- (6-amino) hexyl (meth) acrylamide, and the like, and polyvalent amine compounds.

The type of the polyvalent amine compound is not particularly limited, and examples thereof include low-molecular-weight amines such as ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, and hexamethylenediamine; Polymeric amines such as polypropylene diamine; and polyaminoethylene glycol and polyaminopropylene glycol adducts to trimethylolpropane and glycerin.

具体 Specific examples of the reactive compound (B) having a carboxyl group include a polyolefin modified with an alkyl (meth) acrylic acid and a polyvalent carboxyl compound. Examples of polyolefin-based polycarboxylic compounds include aliphatic polycarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and tricarballylic acid; and carboxyls such as (meth) acrylic acid. Examples include a polycarboxylic acid polymer containing a monomer having a group as a constituent unit.

The reactive compound (B) having an epoxy group is a compound having one, preferably two or more epoxy groups in a molecule, and includes ethylene glycol diglycidyl ether, glycerin diglycidyl ether, and vinylcyclohexene. Dioxide, limonenedioxide, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexylcarboxylate, bis- (3,4-epoxycyclohexyl) adipate and the like can be mentioned.

Specific examples of the reactive compound (B) having a dianhydride group include a polyolefin modified with maleic anhydride or the like.

In the present invention, as the reactive compound (B), a plurality of compounds having a functional group capable of reacting with an epoxy group may be used in combination.

The content of the reactive compound (B) in the release agent of the present invention is preferably 0.001 to 100 parts by weight, more preferably 0.003 parts by weight, based on 1 part by weight of the epoxidized polyolefin elastomer (A). To 70 parts by weight, particularly preferably 0.01 to 50 parts by weight.

The release agent of the present invention is a ratio of the number of functional groups capable of reacting with the epoxy group of the reactive compound (B) to the total number of carbon atoms in the molecule of the reactive compound (B) (functional group number / total carbon number). Is preferably 0.00001 to 0.15. When a reactive compound (B) having a ratio value of more than 0.15 is used, the peeling force tends to increase even after crosslinking. If the reactive compound (B) is less than 0.00001, the effect of crosslinking tends to decrease. A more preferred range of the ratio (number of functional groups / total number of carbons) is 0.00001 to 0.02. The number of functional groups and the total number of carbon atoms of the reactive compound (B) can be determined by a method such as an NMR or IR method.

In the release agent of the present invention, the ratio (A / B) of the total number of epoxy groups of the epoxidized polyolefin elastomer (A) to the total number of functional groups capable of reacting with the epoxy groups of the reactive compound (B) is 0.1. Desirably, it is 01-50. Outside this range, a large amount of unreacted functional groups remain after the crosslinking reaction between the epoxidized polyolefin elastomer (A) and the reactive compound (B), and the peeling force tends to increase. A more preferred range of the ratio (A / B) is 0.05 to 20, and a particularly preferred range is 0.1 to 10.

調整 The method for preparing the release agent and the method for forming the release layer of the present invention are not particularly limited. For example, the epoxidized polyolefin elastomer (A) and the reactive compound (B) are mixed, dissolved in a solvent, applied to the substrate surface, and dried to form a release layer on the substrate.

溶媒 The solvent used is preferably an organic solvent, and considering the efficiency of the drying step, it is preferable to use an organic solvent having a boiling point of 20 to 170 ° C. Specific examples include single or mixed solvents such as toluene, xylene, methyl ethyl ketone, vinyl acetate, heptane, octane, cyclohexane, and tetrahydrofuran.

方法 A known method such as a direct gravure coater, a bar coater, or an air knife coater can be used as a method for coating these substrates. The drying conditions after applying the release agent are not particularly limited, but the drying is usually performed within the range from room temperature to the melting point of the substrate or the glass transition temperature. Drying is preferably performed at room temperature to 100 ° C. for several tens of seconds to several tens of minutes.

(4) After the release agent of the present invention is applied, a crosslinking reaction utilizing an epoxy group of the epoxidized polyolefin elastomer (A) is performed to form a release layer having excellent functions. The conditions for the crosslinking reaction are not particularly limited, and can be appropriately determined depending on the compound to be crosslinked, the type of catalyst, and the type of reaction. The crosslinking reaction is usually performed at 50 ° C to 200 ° C, preferably at 60 ° C to 180 ° C, more preferably at 80 ° C to 150 ° C. The reaction time is not particularly limited, but is preferably 5 seconds to 5 minutes from the viewpoint of maintaining productivity and solvent resistance.

When a crosslinking reaction is performed using a release agent containing the epoxidized polyolefin elastomer (A) and the reactive compound (B), the epoxidized polyolefin elastomer (A) and the reactive compound (B) are used to promote crosslinking. Can be added when dissolving in a solvent or during the heating step. As the catalyst, a catalyst usually used when reacting with an epoxy compound, such as a tertiary amine such as triethylamine, can be used. Although the concentration of the catalyst is not limited, it is desirable to add 10 to 1000 ppm to the crosslinking solution.

The release agent containing the epoxidized polyolefin elastomer (A) can preferably contain a polymerization catalyst for ring-opening polymerization of an epoxy group in the presence of heat and / or active energy rays. Specific examples of such a catalyst include a proton acid and a carbon cation. Further, a compound that generates a proton acid or a carbon cation by heating or active energy rays (UV irradiation or electron beam irradiation) can also be used. Since these polymerization catalysts are particularly effective for the reaction between epoxy groups, it is possible to carry out a crosslinking reaction without adding the reactive compound (B) to the release agent by using these polymerization catalysts. is there. However, even when a polymerization catalyst is used, the reactive compound (B) may be added to the release agent.

The release agent of the present invention may be mixed with an onium salt-based curing catalyst and reacted by heating or irradiation with ultraviolet rays. Examples of the onium salt curing catalyst include ArN ₂ ⁺ Q ⁻ , Y ₃ S ⁺ Q ⁻ or Y ₂ I ⁺ Q ⁻ [wherein, Ar represents an aryl group such as a bis (dodecylphenyl) group, and Y represents an alkyl group. group or the like ant - le group, Q ^- is ^{_{BF 4 -, PF 6, AsF}} 6 -, SbF 6 -, SbCl 6 -, HSO 4 -, Cl - non-basic and nucleophilic anions such as Or a diazonium salt, a sulfonium salt or an iodonium salt.

When the reaction is performed using ultraviolet light, an appropriate ultraviolet light source such as a high-pressure mercury lamp, a low-pressure mercury lamp, and a metal halide lamp is used. The irradiation dose is not particularly limited, but is usually preferably 50 mJ to 5 J / cm ² . At that time, if necessary, a filter or a polyester sheet that blocks ultraviolet rays on the short wavelength side may be used.

添加 The amount of the polymerization catalyst for ring-opening polymerization of these epoxy groups can be determined according to the amount of the reactive compound (B).

基材 The substrate used in the present invention may be any material as long as it has rigidity as a release film. A film of resin or the like can be used, and a film subjected to corona treatment, plasma treatment, flame plasma treatment, or the like may be used. Specific examples include stretched products of polyethylene and polypropylene, stretched products of polyester resins such as polyethylene terephthalate and polybutylene terephthalate, films of polyimide, polycarbonate, polystyrene, cellophane and the like, and sheets thereof. Preferred is a thermoplastic polyester film. In addition, paper and synthetic paper can be used as the base material, and widely used paper such as paper or glassine paper which has been surface-treated with polyethylene or polyvinyl alcohol for surface smoothing.

The thickness of the release layer (a value calculated based on the increase in the weight of the base film after drying and the specific gravity of the release agent as 1.0 g / ml) is usually 0.01 μm to 5 μm, preferably 0 μm. 0.05 μm to 5 μm. If it is less than 0.01 μm, the peeling force is increased due to the influence of the base material, and if it exceeds 5 μm, the coating film tends to be easily peeled off from the film.

離 The release film of the present invention can be used for various applications, and can also be used for an adhesive surface. In particular, the release film of the present invention is preferably used in the process of manufacturing semiconductors and ceramic green sheets. The type of the adhesive surface to which the release film of the present invention is applied is not particularly limited. For example, the present invention can be applied to an adhesive surface made of various adhesives such as an acrylic adhesive, a rubber adhesive, and a polyurethane adhesive. Further, the pressure-sensitive adhesive solution can be transfer-coated on the release layer formed according to the present invention, and dried to form a pressure-sensitive adhesive layer.

For example, the release film of the present invention is used as a release film for an adhesive tape such as an adhesive tape for surface protection or an adhesive tape for dicing used when processing a silicon wafer or the like used for a semiconductor integrated circuit (IC) or the like. can do. Further, the release film of the present invention can be used as a release film for semiconductor resin sealing. That is, the release film of the present invention can be used between the surface to be sealed of the semiconductor chip and the mold.

In the case of producing a ceramic green sheet, a ceramic slurry can be applied on the release layer of the release film of the present invention. The green sheet thus formed on the release film of the present invention can be provided with an electrode made of, for example, palladium, silver, nickel or the like by screen printing or the like. Further, after performing such processing, a process of applying a ceramic slurry again on the ceramic green sheet and providing an electrode may be repeated to form a multilayer structure. After appropriately performing these steps, the release film is peeled from the green sheet, laminated and cut into chips as appropriate, and then baked and processed to obtain capacitors, laminated inductor elements, piezoelectric components, thermistors, varistors, and the like. Ceramic electronic component can be obtained.

離 The release film of the present invention can be preferably used for the production of containers. Examples of a method for producing a container using the release film of the present invention include methods such as thermoforming and blow molding. Thermoforming is a method in which a sheet or the like is heated and softened, and then formed into a mold. As a molding method, a method of forming into a mold shape using a vacuum or a pressurized air and further using a plug as necessary (straight method, drape method, air slip method, snapback method, plug assist method, etc.) or press Molding methods and the like can be mentioned. Various conditions such as the thermoforming temperature, the degree of vacuum, the pressure of the compressed air or the forming speed are appropriately set depending on the shape of the plug, the shape of the mold, the properties of the raw material sheet, and the like. The blow molding method can be performed by a known method, and is formed by a direct blow method, an injection blow method, a hot stretch blow method, a cold stretch blow method, or the like. In the direct blow method, each layer material is simultaneously extruded from a plurality of extruders, a multilayer barison is injected using each layer die, and obtained by multilayer blow molding in which the barison is closed and shaped by a mold, while injection blow method, hot stretching In the blow method and the cold stretch blow method, the film is obtained by heating and shaping using a multilayer preform. Examples of the shape of the container include various cups, trays, dishes, bowl shapes, and the like.

Containers are specifically used for milk containers, fermented milk containers, lactic acid drink containers, milk drink containers and similar containers, etc. listed in the Ministerial Ordinance for Milk, etc., and mineral water containers and tea containers as drink containers. , Juice containers, cola containers, and the like, and food containers include salad oil containers, ketchup containers, mayonnaise containers, lemon juice containers, sauce containers, soy sauce containers, and the like.

(4) The characteristics of the present invention will be described more specifically with reference to examples, comparative examples, and test examples. Materials, usage amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples described below. The film thickness described below is a value determined by calculating the specific gravity as 1.0 g / ml based on the weight change before and after applying and releasing the release agent.

[Production Example 1] Preparation of unmodified polyolefin elastomer Ethylene (70% by weight) and propylene (30% by weight) were polymerized using a metallocene catalyst (dimethylsilylenebiscyclopentadienylzirconium dichloride and methylalumoxane as a cocatalyst). Thus, an ethylene propylene random copolymer was obtained. The weight average molecular weight of the product was 100,000, the molecular weight distribution was 2.3, and the MFR was 2.0 g / 10 min.

[Production Example 2] Preparation of epoxidized polyolefin elastomer 40 g of the ethylene propylene random copolymer obtained in Production Example 1, 1.2 g of glycidyl methacrylate (hereinafter abbreviated as GMA), 2,5-dimethyl-2 as a radical initiator, After dry blending 0.06 g of 5-di-t-butylperoxyhexane, the mixture was kneaded at a reaction temperature of 180 ° C. and a rotation speed of 100 rpm for 3 minutes using a Labo Plastomill kneader (manufactured by Toyo Seiki Seisaku-sho, Ltd.). An ethylene propylene random copolymer having a group was obtained. This polymer was press-molded to form a film, which was quantified by IR spectrum using a calibration curve prepared by characteristic absorption of a carbonyl group at 1,724 cm ^{-1. As} a result, the GMA content was 0.85% by weight.

[Production Example 3] Preparation of epoxidized polyolefin elastomer 40 g of the ethylene propylene random copolymer obtained in Production Example 1, 2.0 g of GMA, and 2,5-dimethyl-2,5-di-t-butyl par as a radical initiator After dry-blending 0.2 g of oxyhexane, the mixture was kneaded at a reaction temperature of 180 ° C. and a rotation speed of 100 rpm for 3 minutes using a Labo Plastomill kneader (manufactured by Toyo Seiki Seisaku-sho, Ltd.) to obtain an ethylene-propylene random copolymer having epoxy groups. A coalescence was obtained. The polymer was press-molded into a film, and the film was quantified using an IR spectrum. As a result, the GMA content was 2.62% by weight.

[Production Example 4] Preparation of Unmodified Polyolefin Elastomer A 1-liter autoclave was replaced with ethylene gas, and 450 mL of degassed and dried toluene and 25 g of similarly degassed and dried 1-hexene were charged. 100 mmol of a methylalumoxane toluene solution (manufactured by Witco) was charged into the system as Al content, and the mixture was stirred at 70 ° C. for 10 minutes, and then 0.1 mmol of a metallocene catalyst (dimethylsilylenebiscyclopentadienyl zirconium chloride) was added. It was pressurized to 0.5 MPa with ethylene gas and polymerized for 2 hours to obtain an ethylene hexene random copolymer. The composition molar ratio of the product determined by ¹ H-NMR was ethylene / hexene = 90/10, the weight average molecular weight of the product determined by GPC was 122,000, the molecular weight distribution was 2.3, and the MFR was 3.5 g / 10 minutes.

[Production Example 5] Preparation of epoxidized polyolefin elastomer 40 g of the ethylene propylene random copolymer obtained in Production Example 1, 1.2 g of an alicyclic epoxy acrylic monomer (manufactured by Daicel Chemical Industries, "Cyclomer A-200"), After dry-blending 0.2 g of 2,5-dimethyl-2,5-di-t-butylperoxyhexane as a radical initiator, using a Labo Plastomill kneader (manufactured by Toyo Seiki Seisaku-sho, Ltd.), the reaction temperature was 180 ° C. The mixture was kneaded at a rotation speed of 100 rpm for 3 minutes to obtain an ethylene-propylene random copolymer having an epoxy group. This polymer was press-molded to form a film, which was quantified using an IR spectrum. As a result, the epoxyacrylic monomer content was 2.7% by weight.

[Production Example 6] Preparation of epoxidized polyolefin elastomer 40 g of the ethylene propylene random copolymer obtained in Production Example 1 and 1.6 g of 4-hydroxybutyl acrylate glycidyl ether (manufactured by Nippon Kasei Co., Ltd .; hereinafter abbreviated as 4-HBAGE). After dry blending 0.06 g of 2,5-dimethyl-2,5-di-t-butylperoxyhexane as a radical initiator, the reaction temperature was 180 ° C. using a Labo Plastomill kneader (manufactured by Toyo Seiki Seisaku-Sho, Ltd.). The mixture was kneaded at a rotation speed of 100 rpm for 3 minutes to obtain an ethylene-propylene random copolymer having an epoxy group. This polymer was press-molded to form a film, which was quantified by IR spectrum using a calibration curve created by characteristic absorption of a carbonyl group of 1,724 cm ^{-1. As} a result, the 4-HBAGE content was 3.5% by weight. .

[Production Example 7] Preparation of hydroxylated polyolefin elastomer 40 g of the ethylene propylene random copolymer obtained in Production Example 1, 1.3 g of 4-hydroxybutyl acrylate (manufactured by Nippon Kasei Co., Ltd .; hereinafter abbreviated as 4-HBA), radical initiation After dry blending 0.06 g of 2,5-dimethyl-2,5-di-t-butylperoxyhexane as an agent, the reaction temperature was 180 ° C. and the number of rotations was using a Labo Plastomill kneader (manufactured by Toyo Seiki Seisakusho). The mixture was kneaded at 100 rpm for 3 minutes to obtain an ethylene propylene random copolymer having a hydroxyl group. The polymer was press-molded to form a film, which was quantified by IR spectrum using a calibration curve prepared by characteristic absorption of a carbonyl group at 1,724 cm ^{-1. As} a result, the 4-HBA content was 3.0% by weight. .

[Example 1]
As the epoxidized polyolefin elastomer (A), 2 g of the GMA-modified ethylene propylene random copolymer obtained in Production Example 2 was used, and as the reactive compound (B), 3.1 mg of hexamethylenediamine (the epoxidized polyolefin elastomer (A)) was used. (Equivalent of 1.1 equivalent of amino group to epoxy group) was prepared and dissolved in 100 g of toluene to obtain a homogeneous solution. This was applied to a polyethylene terephthalate film having a thickness of 38 μm so that the film thickness after drying was 0.2 μm. This was heated at 150 ° C. for 20 seconds by a hot-air circulating drier to form a cured film, thereby producing a release film.

[Example 2]
Except for using 1,6-hexanediol in place of hexamethylenediamine in Example 1, the same operation was performed to produce a release film. 1,6-hexanediol was used in such an amount that the hydroxyl group was 1.1 equivalent to the epoxy group of the epoxidized polyolefin elastomer (A).

[Example 3]
A cured coating was obtained in the same manner as in Example 1, except that the epoxidized polyolefin elastomer (A) was replaced with the GMA-modified ethylene propylene random copolymer obtained in Production Example 3 in place of the GMA-modified elastomer obtained in Production Example 2. Was formed to prepare a release film.

[Example 4]
In Example 1, 2.0 mg (1% by weight based on the polymer) of a cationic polymerization initiator (“SI-25” (sulfonium salt-based compound) manufactured by Sanshin Chemical Industry Co., Ltd.) was used instead of hexamethylenediamine. Except for the above, the same operation was performed to prepare a release film.

[Example 5]
As the unmodified polyolefin elastomer, 1 g of the ethylene hexene copolymer obtained in Production Example 4, 1 g of the GMA-modified ethylene propylene random copolymer obtained in Production Example 3 as the epoxidized polyolefin elastomer (A), and 2.0 mg of the cationic polymerization initiator SI-25 used in Example 4 was prepared, and these were dissolved in 100 g of toluene to obtain a homogeneous solution. This was applied to a polyethylene terephthalate film having a thickness of 38 μm so that the film thickness after drying was 0.2 μm. This was heated at 150 ° C. for 20 seconds by a hot-air circulating drier to form a cured film, thereby producing a release film.

[Example 6]
In Example 1, except that 2.0 mg of polyolefin polyol (manufactured by Mitsubishi Chemical Corporation, "Polytail") and cationic polymerization initiator SI-25 and 2 mg were added as the reactive compound (B) instead of hexamethylenediamine. The same operation was performed to produce a release film.

[Example 7]
In Example 1, a 4-HBAGE-modified ethylene propylene random copolymer obtained in Production Example 6 was used as the epoxidized polyolefin elastomer (A) in place of the GMA-modified elastomer obtained in Production Example 2, and a reactive compound ( Except that 2.0 mg (1% by weight based on the polymer) of a cationic polymerization initiator SI-15 was used instead of hexamethylenediamine as B), the same operation was performed to produce a release film.

Example 8
A release film was prepared in the same manner as in Example 4 except that 2 g of the alicyclic epoxy-modified ethylene propylene random copolymer obtained in Production Example 5 was used as the polyolefin elastomer (A).

[Example 9]
In Example 7, 1.8 g of the 4-HBAGE-modified ethylene propylene random copolymer obtained in Production Example 6 as the polyolefin elastomer (A) and the 4-HBA-modified ethylene propylene random copolymer obtained in Production Example 7 Except that 0.2 g was used, the same operation was performed to prepare a release film.

[Example 10]
A release film was prepared in exactly the same manner as in Example 6, except that 2.0 g of the 4-HBAGE-modified ethylene propylene random copolymer obtained in Production Example 6 was used as the polyolefin elastomer (A).

[Comparative Example 1]
1 g of the ethylene hexene copolymer obtained in Production Example 4 and 1 g of the ethylene propylene random copolymer obtained in Production Example 1 were prepared, and these were dissolved in 100 g of toluene to obtain a homogeneous solution. This was applied to a polyethylene terephthalate film having a thickness of 38 μm so that the film thickness after drying was 0.2 μm. Thereafter, this was heated at 120 ° C. for 1 minute by a hot air circulation type drier to form a cured film, thereby forming a release film.

[Comparative Example 2]
1 g of the ethylene propylene random copolymer obtained in Production Example 1 was dissolved in 50 g of toluene to obtain a homogeneous solution. This was applied to a polyethylene terephthalate film having a thickness of 38 μm so that the film thickness after drying was 0.4 μm. This was heated at 120 ° C. for 1 minute with a hot-air circulating dryer to form a cured film, thereby producing a release film.

[Test example]
<Peeling test>
The release films obtained in the above Examples and Comparative Examples were cut into a width of 30 mm and a length of 150 mm, and a commercially available adhesive tape having a width of 25 mm (Nitto Tape No. 502, manufactured by Nitto Denko Corporation) was cut. A rubber roller having a weight of 2 kg was reciprocated once and pressed. Thereafter, the adhesive tape was fixed with a tensile tester, the separator was peeled off at 180 ° at a speed of 300 mm / min at 23 ° C., and the force required for the peeling (average value of five samples) was measured. Table 1 shows the results.

<Solvent resistance test>
The release films obtained in the above Examples and Comparative Examples were immersed in toluene for 10 minutes, taken out and dried at room temperature, and then subjected to the above-mentioned peeling test to measure the peeling force. Table 1 shows the results.

<Heat peel test>
After the pressure-sensitive adhesive tape was pressed in the above-described peeling test, it was kept at 100 ° C. for 1 hour, and then cooled at room temperature, and then the peeling force was measured using a tensile tester. Table 1 shows the results.

<Love-off property>
The release layer obtained from the present invention was rubbed with the pad of a finger, and its scratching property was visually confirmed.
：: No or almost no whitening is observed.
Δ: slight whitening is observed ×: clear whitening is observed

<Transfer coating test>
On the release layer of the release film obtained in Example 10 and Comparative Example 1, 100 parts by weight of an adhesive liquid (manufactured by Soken Chemical Co., Ltd., SK Dyne SK1604N) was added to an isocyanate curing agent (manufactured by Soken Chemical Co., Ltd.) , L-45), and the mixture was made uniform by adding 1.5 parts by weight using a 100 μm applicator manufactured by Taiyo Kiki Co., Ltd. so that the thickness of the adhesive liquid was 100 μm and the width was 8 cm. After 2 seconds from the application, the film was dried in Safe Ben Dryer N50-S5 manufactured by Satake Chemical Instruments Co., Ltd. heated to 100 ° C. for 2 minutes, taken out and cooled to room temperature. Then, after 2 minutes, the pressure-sensitive adhesive substrate is placed on the pressure-sensitive adhesive layer, and reciprocated once at a speed of 30 cm / min on a 2 kg roller pressure-sensitive adhesive substrate, so that the pressure-sensitive adhesive layer and the pressure-sensitive adhesive substrate are pressed and released. An adhesive having a pressure-sensitive adhesive sheet provided on the sheet was obtained. This adhesive sheet was cut into a width of 30 mm and a length of 150 mm, and a commercially available adhesive tape having a width of 25 mm (Nitto Tape No. 502, manufactured by Nitto Denko Corporation) was reciprocated through a rubber roller of 2 kg in weight once. And crimped. Thereafter, the adhesive tape was fixed by a tensile tester, the separator was peeled off at 180 ° at a speed of 300 mm / min at 23 ° C., and the force required for the peeling (mean value of five samples, unit: mN / cm) was measured. did. Table 2 shows the results.

Claims (15)

A release agent containing a polyolefin elastomer (A) having an epoxy group. The release agent according to claim 1, which comprises a reactive compound (B) having a functional group capable of reacting with an epoxy group. The mold release agent according to claim 2, wherein the functional group capable of reacting with the epoxy group of the reactive compound (B) is a hydroxyl group, an amino group, a carboxyl group, an epoxy group or an acid anhydride group. The release agent according to claim 2, wherein the reactive compound (B) is a polyolefin having a hydroxyl group, an amino group, a carboxyl group, or an epoxy group. The release agent according to any one of claims 1 to 4, further comprising a polymerization catalyst for subjecting the epoxy group of the polyolefin elastomer (A) to ring-opening polymerization in the presence of heat and / or active energy rays. A step of applying the release agent according to any one of claims 1 to 5 to at least one surface of a base film to form a release agent-containing layer, and heating the release agent-containing layer. A method for producing a release film having a release layer on at least one side, comprising a step of ring-opening polymerizing an epoxy group of the polyolefin elastomer (A). A step of applying the release agent according to any one of claims 2 to 5 to at least one surface of a base film to form a release agent-containing layer, and heating the release agent-containing layer. A method for producing a release film having a release layer on at least one side, comprising a step of reacting a polyolefin elastomer (A) with a reactive compound (B). A release film having a release layer formed by curing the release agent according to any one of claims 1 to 5 on at least one surface of the base film. The release film according to claim 8, wherein the base film is a thermoplastic polyester film. A release paper having a release layer formed by curing the release agent according to claim 1 on at least one side of the paper. The release film according to claim 8, which is used in a semiconductor manufacturing process. The release film according to claim 8, which is used in a process of manufacturing a ceramic green sheet. An adhesive tape having a release layer formed by curing the release agent according to any one of claims 1 to 5 on at least one surface of a base film. A surface protection film having a release layer formed by curing the release agent according to any one of claims 1 to 5 on at least one surface of the base film. A container obtained from a resin sheet having a release layer obtained by curing the release agent according to claim 1 on at least one surface.