KR20210120121A - Laminated film and method for producing same - Google Patents

Abstract

A laminated film having a thermoplastic resin film and a resin layer containing a silicone resin (the resin layer is referred to as a release layer), wherein the release layer is in at least one outermost layer of the laminated film, and the press-fitting measured from the release layer side A laminate film having an elastic modulus of 100 N/mm 2 or more, and an arithmetic mean roughness (Ra) of the surface of the release layer of 1 to 50 nm. Provided is a laminated film excellent in releasability to an adhesive or releasability to a ceramic slurry, and excellent in smoothness, transferability, and friction resistance.

Description

Laminated film and its manufacturing method TECHNICAL FIELD

The present invention relates to a laminated film which is excellent in the releasability to an adhesive and the releasability of a ceramic slurry, and is also excellent in smoothness, transferability and friction resistance, and a method for producing the same.

DESCRIPTION OF RELATED ART Conventionally, the film which has releasability is used as carrier films, such as a protective film of the adhesive material layer in an adhesive product, and a ceramic sheet. As these release films, the film in which the layer which consists of mold release agents, such as a silicone resin, a fluororesin, a long-chain alkyl group-containing compound, and an olefin resin, was formed as a mold release layer on a thermoplastic resin film. Among these, the film which has a release layer which consists of a silicone resin from the point of industrial productivity and heat resistance is used universally.

The following are mentioned as a characteristic calculated|required of a release film.

First, light-peelable (excellent peeling force) from which an adhesive layer or a ceramic sheet can peel easily is calculated|required. In addition, it is important that the mold release layer is sufficiently stable and strong with the thermoplastic resin film from the viewpoint of preventing poor performance of the adherend (laminated body) due to the release component being transferred to the adherend (laminated body). In addition, in recent years, with the miniaturization and refinement of electronic materials, when used as a carrier film, a smooth surface of the release layer is required so that the uneven shape of the surface of the release film is not transferred to the ceramic sheet.

As a film excellent in the peeling force of a release layer, the method of adding particle|grains to the release layer which consists of a silicone resin and adjusting peeling force is known (patent document 1).

Further, as a film excellent in smoothness of the release layer, a method of suppressing the addition reaction of the silicone resin by using a crosslinking inhibitor in addition to the silicone resin in combination and suppressing the generation of protrusions due to aggregation of the silicone resin is known (Patent Document 2) .

Moreover, as a film excellent in peeling force and smoothness, the method of containing a silicone resin and a hydrophilic polyester resin as a component in a release layer is known (patent document 3).

Japanese Patent Laid-Open No. 2011-173362 Japanese Patent Laid-Open No. 2013-208810 Japanese Patent No. 5319328

In the method described in patent document 1, in order to make the release film surface into a rough surface intentionally, it has the subject that coexistence with smoothness is difficult.

In addition, in the method described in Patent Document 2, since unreacted substances increase by suppressing the addition reaction of the silicone resin, there is a problem that the mold release component of the release layer is transferred to the adherend (adhesive layer or laminate). When the release component of the release layer is transferred to the adherend (adhesive layer or laminate), the peeling force of the release layer is biased, or when the adherend to which the release component is attached is post-processed, poor processing (crawling, etc.) happens In addition, in this application, the characteristic in which the release component of a release layer is hard to transfer to a to-be-adhered body (adhesive layer or laminated body) is called transferability. This transferability can be evaluated by the difference of the adhesive force at the time of the peeling force of the initial stage of an adhesive layer, and the adhesive tape once peeled after sticking an adhesive tape on a release layer, and sticking again and peeling.

In addition, in the method described in Patent Document 3, since it is necessary to include a hydrophilic group containing a sulfur element or a nitrogen element in order to make the polyester resin hydrophilic, curing inhibition of the silicone resin by catalyst poison occurs, and the silicone resin It has the subject that an uncured material is transcribe|transferred to a to-be-adhered body.

Then, the subject of this invention is excellent in the peelability with respect to the adhesive agent and the peelability with respect to a ceramic slurry, and it is providing the film excellent in smoothness, transferability, and abrasion resistance.

The laminated|multilayer film by this invention and its manufacturing method have the following structures.

(1) A laminated film having a thermoplastic resin film and a resin layer containing a silicone resin (the resin layer is referred to as a release layer), wherein the release layer is in at least one outermost layer of the laminated film, and from the release layer side The laminated film whose measured indentation modulus is 100 N/mm<2> or more, and arithmetic mean roughness (Ra) of the said mold release layer surface is 1-50 nm.

(2) The laminated|multilayer film as described in (1) whose peeling force change (peel force (P2) after abrasion process / peeling force (P1) before abrasion process) before and behind the said release layer rubbing process is 30 or less.

(3) The laminated|multilayer film of Claim 1 or 2 in which resin which comprises the said mold release layer contains the hydroxyl-containing compound whose molar mass is 300 g/mol or less containing two or more hydroxyl groups in 1 molecule.

(4) The content of the silicone resin contained in the release layer is 60% by weight or more with respect to the entire release layer, and the content of the hydroxyl group-containing compound contained in the release layer is 5 to 40 parts by weight when the silicone resin is 100 parts by weight. , the laminated film described in (3)

(5) The laminated|multilayer film as described in (3) or (4) in which the said hydroxyl-containing compound contains the at least 1 sort(s) of compound chosen from glycol, sugar alcohol, and a sugar alcohol derivative.

(6) The laminated|multilayer film in any one of (1)-(5) whose said silicone resin is an addition-curable silicone resin.

(7) The laminated|multilayer film in any one of (1)-(6) which has a mold release layer directly on at least single side|surface of a thermoplastic resin film.

(8) A coating liquid containing a silicone resin is applied to at least one side of the thermoplastic resin film before crystal orientation is complete, and then the thermoplastic resin film is stretched in at least one axial direction, and the thermoplastic resin film is subjected to heat treatment And the manufacturing method of the laminated|multilayer film in any one of (1)-(7) including the process of completing the crystal orientation of this thermoplastic resin film.

(9) The manufacturing method of the laminated|multilayer film as described in (8) containing the hydroxyl-containing compound whose molar mass is 300 g/mol or less which contains 2 or more hydroxyl groups in 1 molecule in the said coating liquid.

(10) The manufacturing method of the laminated|multilayer film as described in (9) whose boiling point of the said hydroxyl-containing compound is 200 degreeC or more

ADVANTAGE OF THE INVENTION According to this invention, it is excellent in the peelability with respect to the peelability with respect to an adhesive, and a ceramic slurry, and can provide the laminated|multilayer film excellent in smoothness, transferability, and friction resistance.

The laminated film of this invention is a laminated|multilayer film which has a release layer containing a thermoplastic resin film and a silicone resin, The said release layer is in at least one outermost layer of a laminated|multilayer film, The ultra-fine measured from the release layer side of the laminated|multilayer film. It is a laminated|multilayer film whose indentation elastic modulus is 100 N/mm<2> or more computed from an indentation hardness tester, and arithmetic mean roughness (Ra) of a release layer is 1-50 nm.

<Film used as a base material>

Hereinafter, the laminated|multilayer film of this invention are demonstrated in detail.

The laminated film of this invention is a laminated|multilayer film which has a thermoplastic resin film used as a base material, and the mold release layer containing a silicone resin, The said mold release layer is in at least one outermost layer of laminated|multilayer film, The release layer side of the laminated|multilayer film It is a laminated|multilayer film whose indentation elastic modulus is 100 N/mm<2> or more, and arithmetic mean roughness (Ra) of a mold release layer is 1-50 nm computed from the measured ultrafine indentation hardness tester.

The laminated|multilayer film of this invention WHEREIN: The thermoplastic resin film used as a base film is a generic term for the film which uses a thermoplastic resin, and melts or softens by heat. Examples of the thermoplastic resin include a polyester resin, a polypropylene resin, a polyolefin resin such as a polyethylene film, a polylactic acid resin, a polycarbonate resin, an acrylic resin such as a polymethacrylate resin or a polystyrene resin, a polyamide resin such as a nylon resin, A polyvinyl chloride resin, a polyurethane resin, a fluororesin, polyphenylene resin, etc. are mentioned. The thermoplastic resin used for the thermoplastic resin film may be a monomer or a copolymer may be sufficient as it. Moreover, you may use several resin.

Representative examples of thermoplastic resin films using these thermoplastic resins include polyester films, polyolefin films such as polypropylene films and polyethylene films, polylactic acid films, polycarbonate films, acrylic films such as polymethacrylate films and polystyrene films, nylon Polyamide films, such as a polyvinyl chloride film, a polyurethane film, a fluorine-type film, a polyphenylene sulfide film, etc. are mentioned.

Although the thermoplastic resin film in this invention is not specifically limited, A polyester film and polyethylene film excellent in mechanical strength and workability are preferable. In particular, a polyester film is preferable from the point of heat resistance and a mechanical characteristic.

Then, below in this invention, the polyester resin which comprises the polyester film used especially suitably as a thermoplastic resin film is demonstrated in detail.

In the present invention, the polyester constituting the polyester film serving as the substrate is a generic term for polymers in which an ester bond produced by polycondensation of a dicarboxylic acid and a diol serves as a main bond chain of the main chain. Preferred examples of polyester include ethylene terephthalate, ethylene-2,6-naphthalate, butylene terephthalate, propylene terephthalate, and 1,4-cyclohexanedimethylene phthalate. These constituent resins may be used alone or in combination of two or more. The intrinsic viscosity of the polyester (measured in α-chlorophenol at 25°C) is preferably 0.4 to 1.2 dl/g, more preferably in the range of 0.5 to 0.8 dl/g for carrying out the present invention. It is preferable in

Moreover, it is preferable that it is a biaxially-oriented polyester film as a polyester film used as a base material of this invention. Here, "biaxial orientation" means showing a pattern of biaxial orientation by wide-angle X-ray diffraction. A biaxially-oriented polyester film can be obtained by generally extending|stretching a polyester sheet in an unstretched state about 2.5 to 5 times, respectively in the sheet longitudinal direction and the width direction, and heat-processing after that to complete crystal orientation.

In addition, the base film used for the laminated|multilayer film of this invention may be a single|mono layer film, or a laminated|multilayer film of two or more layers may be sufficient as it. For example, it is a composite film which has an inner layer part and a surface layer part, Comprising: A laminated|multilayer film in which the layer in which the particle|grains were contained only in the surface layer part was formed without containing particle|grains substantially in the inner layer part is mentioned.

In addition, in the resin composition constituting the film serving as the substrate, various additives such as antioxidants, heat-resistant stabilizers, weathering stabilizers, ultraviolet absorbers, organic lubricants, pigments, dyes, organic or inorganic fine particles, fillers, antistatic agents, A nucleating agent, a crosslinking agent, etc. may be added to the extent which does not deteriorate the characteristic.

Although the layer thickness of the film used as the base material of this invention is suitably selected according to a use, Usually, Preferably it is 5-500 micrometers, More preferably, it is 10-300 micrometers, More preferably, it is 10-50 micrometers.

<Release layer>

The laminated film of the present invention has a release layer containing a silicone resin (A) in at least one outermost layer of the laminated film, the indentation modulus measured from the release layer side is 100 N/mm 2 or more, and the arithmetic mean roughness of the release layer It is necessary that (Ra) is 1-50 nm. In addition, indentation elastic modulus is calculated|required by the ultra-micro indentation hardness tester. It will be described later in detail.

The silicone resin (A) used in this invention is not specifically limited, Well-known types of silicone resins, such as an addition-curable silicone resin and a condensation-curable silicone resin, can be used. Among these, it is preferable to use an addition-curable silicone resin since generation|occurrence|production of a by-product is small. Hereinafter, the addition-curable silicone resin is demonstrated in detail.

The addition-curable silicone resin used in the present invention refers to a polysiloxane resin component (Aa) having at least two unsaturated groups in one molecule as a component, and a polysiloxane resin component (Ab) having at least two hydrosilyl groups in one molecule. It is a silicone resin produced by reaction. In addition, the hydrosilyl group in this specification means the functional group in which the hydrogen atom is couple|bonded with the silicon atom directly.

In addition, in the present invention, in addition to the polysiloxane resin components (Aa) and (Ab), it is an addition-curable silicone resin synthesized from a raw material containing a polysiloxane resin component (Ac) containing polydimethylsiloxane as a main component, Since low peeling can be achieved, it is more preferable. The polysiloxane resin component (Ac) having polydimethylsiloxane as a main component as used herein refers to a polysiloxane resin _{containing 50 mol% or more of "-Si(CH 3} ) ₂ O-" units (bifunctional components) in one molecule. It is a dimethylsiloxane resin component.

It is required that the laminated|multilayer film of this invention have the indentation elastic modulus measured from the mold release layer side 100 N/mm<2> or more. The indentation modulus is an index indicating to what extent the release layer elastically deforms. A high indentation modulus means that the release layer is rigid, and a low indentation modulus indicates that the release layer is flexible. In addition, the indentation elastic modulus referred to in this application is computed from the ultrafine indentation hardness tester by the method mentioned later. In this method, by measuring the indentation modulus with a small load, the indentation modulus (to what extent elastic deformation) of the release layer can be measured without being affected by the thermoplastic resin film as the base film. The indentation modulus is preferably 500 N/mm 2 or more and 6000 N/mm 2 or less, and more preferably 1000 N/mm 2 or more and 5000 N/mm 2 or less. When the indentation elastic modulus is less than 100 N/mm 2 , elastic deformation of the release layer occurs when the pressure-sensitive adhesive layer is peeled off, and the peeling force deteriorates. In order to make an indentation elastic modulus into the said range, the method of adjusting the composition of the silicone resin (A) used by a mold release layer, and the method of adding a crosslinking component to a mold release layer are mentioned.

As a method of adjusting the composition of the silicone resin, a polysiloxane resin component (Aa) having at least two unsaturated groups in one molecule, which is a component of the silicone resin, and a polysiloxane resin component (Ab) having at least two hydrosilyl groups in one molecule A method of increasing the addition reaction point of the polysiloxane resin or increasing the content of the "-Si(CH ₃ )O ₂ -" unit (trifunctional component) contained in the polysiloxane resin component is mentioned.

Silicone by increasing the number of unsaturated groups in the polysiloxane resin component (Aa) having at least two unsaturated groups in one molecule and the number of hydrosilyl groups in the polysiloxane resin component (Ab) having at least two hydrosilyl groups in one molecule The crosslinking points in the resin increase, and a three-dimensional crosslinking structure is obtained. As a result, the indentation modulus of the release layer increases.

Furthermore, since the crosslinked structure becomes three-dimensional even by increasing the content of _{the "-Si(CH 3} )O ₃ -" unit (trifunctional component) contained in the polysiloxane resin constituents (Aa) and (Ab), the release layer The indentation modulus of is increased.

Moreover, as a method of adding a crosslinking component to a mold release layer, the method of adding crosslinking agents, such as an epoxy resin, is mentioned. The addition of the crosslinking agent improves the rigidity of the release layer and increases the indentation modulus.

Among these, the method of adjusting the composition of a silicone resin is preferable as a method of adjusting an indentation elastic modulus without worsening peeling force or transferability.

The polysiloxane resin component (A-a) having at least two unsaturated groups in one molecule is preferably a polysiloxane resin having an alkenyl group, and examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, and a pentenyl group. Among these, a vinyl group is the most preferable.

As the polysiloxane resin component (Ab) having at least two hydrosilyl groups in the molecule, poly(dihydrogensiloxane), poly(methylhydrogensiloxane), poly(ethylhydrogensiloxane), poly(phenylhydrogensiloxane), poly[(methylhydrogensiloxane)(dimethylsiloxane)] copolymer, poly[(methylhydrogensiloxane)(ethylmethylsiloxane)] copolymer, poly[(methylhydrogensiloxane)(diethylsiloxane)] copolymer, poly[(methylhydrogensiloxane)(hexylmethylsiloxane)] copolymer, poly[(methylhydrogensiloxane)(octylmethylsiloxane)] copolymer, poly[(methylhydrogensiloxane)(octadecylmethylsiloxane)]co Polymer, poly[(methylhydrogensiloxane) (octadecylmethylsiloxane)] copolymer, poly[(methylhydrogensiloxane) (phenylmethylsiloxane)] copolymer, poly[(methylhydrogensiloxane) (diethoxysiloxane) ] copolymer and poly[(methylhydrogensiloxane)(dimethoxysiloxane)] copolymer.

The method for preparing the polysiloxane resin component (Aa) having at least two unsaturated groups in one molecule and the polysiloxane resin component (Ab) having at least two hydrosilyl groups in the molecule is not particularly limited, for example, dimethyldichlorosilane, Polycondensation and re-equilibration of chlorosilanes necessary for a desired structure such as diphenyldichlorosilane, methylphenyldichlorosilane, dimethylvinylchlorosilane, or dimethyldimethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, It can obtain by co-hydrolyzing the alkoxysilanes necessary for a desired structure, such as dimethylvinylmethoxy, and performing polycondensation and re-equilibration reaction.

The main chain structure of the polysiloxane resin component (Aa) having at least two unsaturated groups in one molecule and the polysiloxane resin component (Ab) having at least two hydrosilyl groups in the molecule may be linear, branched or cyclic. However, from the point of peelability, linear form is preferable.

In the present invention, the content of the silicone resin (A) in the release layer is preferably 50% by weight or more with respect to the entire release layer, more preferably 60% by mass or more, still more preferably 70% by weight or more and 100% by weight or less. it is preferable Since the silicone resin (A) has a low surface energy among resins, it is arranged on the surface layer (so-called air layer) side among the mold release layers. Therefore, when content of the silicone resin (A) in a mold release layer is 50 weight% or more, it becomes possible to express high mold release property. On the other hand, when it is less than 50 weight%, the arrangement|sequence of the silicone resin (A) with respect to the surface layer of a mold release layer may become inadequate, and peeling force may deteriorate.

In the laminated|multilayer film of this invention, it is required that arithmetic mean roughness (Ra) of a mold release layer is 1-50 nm. Preferably it is 1-30 nm, More preferably, it is 1-20 nm. When the arithmetic mean roughness (Ra) of the release layer exceeds 50 nm, heavy peeling occurs due to the anchor effect, for example, when used as a release film of a ceramic slurry, there is a practical problem. In addition, when the arithmetic mean roughness (Ra) of the release layer exceeds 50 nm, since the unevenness of the release layer is transferred to the laminate, there is a problem when used as a carrier film.

As a method for making the surface roughness of the release layer within the above range, a method of applying a coating liquid containing a silicone resin to a thermoplastic resin film and heating the coating liquid to soften the evaporation rate when evaporating the coating liquid can be heard This method is particularly effective when the diluent solvent of the coating liquid containing the silicone resin is an organic solvent, and a preferred method is to use a plurality of solvents having different boiling points as the diluent solvent to slow the evaporation rate of the solvent. have.

On the other hand, when the dilution solvent is an aqueous solvent, a method in which the release layer contains a hydroxyl group-containing compound (hydroxyl group-containing compound (B)) containing two or more hydroxyl groups in one molecule and having a molecular weight of 300 g/mol or less (hydroxyl group-containing compound (B)) can be mentioned. have. Among them, a silicone resin and a coating solution containing a hydroxyl group-containing compound having two or more hydroxyl groups in one molecule and having a molecular weight of 300 g/mol or less is applied by an in-line coating method, and then stretched in at least one axial direction. , heat treatment to form a release layer comprising a silicone resin and a hydroxyl group-containing compound containing two or more hydroxyl groups in one molecule and having a molecular weight of 300 g/mol or less, defects or cracks are unlikely to occur in the release layer, and smoothness is reduced It is preferable because an excellent release layer can be formed.

Next, a hydroxyl group-containing compound containing two or more hydroxyl groups in one molecule and having a molecular weight of 300 g/mol or less will be described.

The laminated film of the present invention contains a hydroxyl group-containing compound (B) containing two or more hydroxyl groups in one molecule and two or more hydroxyl groups in one molecule having a molecular weight of 300 g/mol or less in resin constituting the release layer. It is preferable to do When the resin constituting the release layer contains the hydroxyl group-containing compound (B), defects and cracks are less likely to occur in the release layer, resulting in a release layer excellent in smoothness. As a reason this effect is acquired, it is estimated that it is based on the following two reasons.

First of all, since the hydroxyl group forms a hydrogen bond with a water molecule, the hydroxyl group-containing compound (B) containing two or more hydroxyl groups in one molecule is a compound with very high hydrophilicity. By using the hydroxyl group compound (B) containing two or more hydroxyl groups, in the drying step when an aqueous solvent is used as a solvent for the silicone resin (A) composition, the high hydrophilicity of the hydroxyl group-containing compound (B) causes water in the coating film. It is possible to maintain the fluidity of the coating film. As a result, rapid evaporation of water during drying can be suppressed, the arithmetic mean roughness of the release layer can be suppressed, peelability can be reduced, and smoothness can be improved.

As a second reason, when the release layer is laminated by the in-line coating method, the water retention rate of the coating film when the coating liquid undergoes a drying process to become a coating film by including the hydroxyl group-containing compound (B) in the coating liquid increases, so that the drawability is improved. and, as a result, the formation of the uneven structure of the coating film can be suppressed. As a result, the arithmetic mean roughness of the release layer can be set within the required range of the present invention.

It is preferable that the hydroxyl-containing compound (B) used by this invention has three or more hydroxyl groups in 1 molecule from the point of hydrophilicity improvement. More preferably, it is more preferable that it is 6 or more.

Moreover, since a hydroxyl-containing compound (B) becomes possible to exist in a fine dispersion state in a coating film as molecular weight is 300 g/mol or less, and hydrophilicity improves, it is preferable. More preferably, it is 200 g/mol or less.

In this invention, it is preferable that the boiling point of a hydroxyl-containing compound (B) is 200 degreeC or more, More preferably, it is 250 degreeC or more. When a boiling point is less than 200 degreeC, evaporation of the solvent in a drying process may become rapid, or the crack suppression effect in an extending process may not fully be acquired.

The hydroxyl group-containing compound (B) used in the present invention preferably contains at least one compound selected from glycols, sugar alcohols, and sugar alcohol derivatives in terms of evaporation rate and water holding capacity.

The glycol used as the hydroxyl group-containing compound (B) in the present invention is an alcohol in which two carbon atoms of a chain aliphatic hydrocarbon or a cyclic aliphatic hydrocarbon each have a hydroxyl group.

Specific examples of the glycol include ethylene glycol, diethylene glycol, propylene glycol, butylene glycol and polyethylene glycol. These may be used by 1 type and may use 2 or more types of mixtures. Among these, ethylene glycol and diethylene glycol are easy to obtain industrially and are preferable.

The sugar alcohol or sugar alcohol derivative used as the hydroxyl group-containing compound (B) in the present invention is an alcohol having two or more hydroxyl groups obtained by reducing the carbonyl group of a sugar molecule, and a derivative thereof. In addition, in a sugar molecule having three or more carbonyl groups, at least two or more carbonyl groups are reduced, and when it has two or more hydroxyl groups, it is used as the hydroxyl group-containing compound (B) in the present invention even if other carbonyl groups remain without reduction. It is assumed that it corresponds to the sugar alcohol used. In addition, the sugar in the present invention is _{a generic term for carbohydrates having 3 or more carbon atoms represented by C m} H _n O _p (m, n, and p are integers of 3 or more, and n is 2 multiples of p) in the molecular formula, It has a carbonyl group, such as an aldehyde group and a ketone group, in a molecule|numerator. Incidentally, the sugar alcohol derivative used as the hydroxyl group-containing compound (B) in the present invention is a compound in which a part of the hydroxyl group is a salt in a sugar alcohol having three or more hydroxyl groups, and a compound in which a part of the hydroxyl group reacts with another functional group. points to However, it is necessary to have at least two or more hydroxyl groups.

Specific examples of the sugar alcohol used as the hydroxyl group-containing compound (B) include glycerin, erythritol, threitol, arabinitol, xylitol, ribitol, iditol, galactitol, glucitol, mannitol, bolemitol, Perceitol, inositol, etc. are mentioned. Examples of the sugar alcohol derivative include derivatives of these sugar alcohols. These may be used by 1 type and may use 2 or more types of mixtures. Among these, glycerol, xylitol, glucitol, mannitol, and erythritol are easy to obtain industrially and are preferable. In addition, if the sugar alcohol or sugar alcohol derivative has high solubility in the solvent, it is preferable to use one having high solubility in the solvent because the sugar alcohol or sugar alcohol derivative can be stably maintained in the solvent even at a high temperature.

In this invention, when the ratio of the hydroxyl-containing compound (B) contained in a mold release layer makes 100 weight part of silicone resins (A) contained in a mold release layer, it is preferable that they are 5 weight part or more and less than 40 weight part. In the case of less than 5 parts by weight, the effect of reducing the arithmetic mean roughness of the release layer may be insufficient. Moreover, when it exceeds 40 weight part, the ratio of the silicone resin (A) contained in a mold release layer may become low and it may become heavy peeling.

The laminated film of the present invention is a laminated film having a thermoplastic resin film and a release layer containing a silicone resin, wherein the release layer is a laminated film in at least one outermost layer of the laminated film, but the release layer is at least of the thermoplastic resin film It is preferable to have it directly on one side. By having a mold release layer directly on a thermoplastic resin film, since the heat processing performed until laminated|multilayer film is obtained can be decreased, the thermal damage of the thermoplastic resin film used as a base film can be reduced, and the smoothness of a base film can be maintained. can Moreover, since it can suppress that the oligomer which arises from a base film precipitates on the film surface, it is also preferable. Moreover, since a release film can be manufactured cheaply, it is preferable.

In this invention, it is preferable that peeling force change P2/P1 (peel force after abrasion process (P2)/peel force (P1) before abrasion process) before and after carrying out abrasion treatment of a release layer is 30 or less. In addition, the abrasion process as used in this invention shows the process of rubbing the mold release layer surface 10 reciprocally using a nonwoven fabric (NT-4 made from Ozu Sangyo Co., Ltd. Heise) at a load of 500 g/cm<2>. In addition, peeling force is calculated|required by the measuring method mentioned later. When P2/P1 exceeds 30, since the adhesiveness of a release layer and a thermoplastic film is insufficient, in the process of processing an adhesive layer etc., since deterioration of peeling force is seen, it may become a practical problem. More preferably, they are 10 or more and 25 or less.

As a method of setting the peel force change P2/P1 before and after the release layer rubbing treatment to 30 or less, a method of forming an anchor coat layer between the thermoplastic resin film and the release layer, or a thermoplastic resin before crystal orientation is completed A method of forming by a so-called in-line coating method in which a coating solution containing a silicone resin is applied to at least one side of the film, followed by stretching, and heat treatment to laminate a release layer is exemplified.

Among these, the method of forming a release layer by the inline coating method from the point of reduction of the thermal damage of a base film and the adhesive point of a thermoplastic resin film and a release layer is preferable.

Here, the adhesiveness of a thermoplastic resin film and a mold release layer is demonstrated.

When a release layer is formed on a thermoplastic resin film by a normal off-coating method, since the release layer made of a silicone resin having a low surface energy lacks adhesion to the film, when the film roll is rewound, the release layer is The problem that peeling off and peeling force deteriorates may arise. However, when the release layer is laminated by the inline coating method, a very small amount of the resin composition is impregnated into the resin film by applying the resin composition to the thermoplastic resin film before the completion of crystal orientation, and adhesion between the release layer and the thermoplastic resin film is imparted. can do. As a result, excellent peeling force can be maintained.

As thickness of the mold release layer in this invention, it is preferable that they are 5 nm or more and 500 nm or less, More preferably, they are 20 nm or more and 400 nm or less, More preferably, they are 50 nm or more and 300 nm or less. When the thickness of a mold release layer is less than 5 nm, it becomes difficult to make the thickness of a mold release layer uniform, and deterioration of peeling force may arise. On the other hand, when the thickness of a mold release layer exceeds 500 nm, hardening may become inadequate and transferability may deteriorate.

The laminated|multilayer film of this invention has the characteristic that there is little transcribe|transfer of the mold release component in a mold release layer to a to-be-adhered body (adhesive layer or laminated body). It becomes possible to reduce the dispersion|variation in the peeling force of a mold release layer by having this characteristic. Furthermore, after peeling the laminated|multilayer film of this invention from a to-be-adhered body, when post-processing a to-be-adhered body further, defects, such as crawling of a to-be-adhered body, can be suppressed. Therefore, the laminated|multilayer film of this invention can be used suitably for the use of a process film.

Moreover, it is preferable that the peeling force after carrying out a high temperature aging process of the laminated|multilayer film of this invention is less than 0.5 N/50 mm. In addition, the high temperature aging process as used in this invention shows the process of leaving laminated|multilayer film still in the environment of 70 degreeC 40%RH for 24 hours. More preferably, it is less than 0.4 N/50 mm, More preferably, it is less than 0.3 N/50 mm. When an adhesive is used as an adherend, in order to complete the curing reaction of the adhesive, it may be left still for several days to one week at a high temperature of close to 70°C. The laminated|multilayer film whose peeling force after a high temperature aging process is the said range can show favorable peeling characteristics also with respect to the adhesive which hardening reaction takes a long time at high temperature.

In addition, since the laminated film of the present invention has a high indentation elastic modulus of 100 N/mm 2 of the release layer, the fluidity of the coating film at high temperature is low, and it is difficult to contact or compatibilize with the pressure-sensitive adhesive. It is estimated that In addition, in the case of laminating the release layer by in-line coating, since high-temperature heat treatment is performed, since the addition reaction of the release layer is completed, the reaction with the pressure-sensitive adhesive does not proceed at high temperature, so even after high-temperature aging treatment, initial peeling I think it's holding power.

<Method of Forming a Release Layer>

In this invention, after apply|coating the coating liquid containing a silicone resin to at least single side|surface of a thermoplastic resin film, it is preferable to form a mold release layer by drying. In this invention, when making a coating liquid contain a solvent, it is preferable to use an aqueous solvent as a solvent. By using an aqueous solvent, rapid evaporation of the solvent in the drying process can be suppressed, a uniform release layer can be formed, and it is excellent in terms of environmental impact.

Here, the aqueous solvent refers to water or water, alcohols such as methanol, ethanol, isopropyl alcohol and butanol, ketones such as acetone and methyl ethyl ketone, and glycols such as ethylene glycol, diethylene glycol and propylene glycol. It indicates that a soluble organic solvent is mixed in an arbitrary ratio.

Although either of an in-line coating method and an off-coating method can be used as the coating method with respect to the film of a coating liquid, an in-line coating method is preferable. The in-line coating method is a method of applying within the process of manufacturing a thermoplastic resin film. Specifically, it refers to a method in which a thermoplastic resin is melt-extruded, followed by biaxial stretching, heat treatment, and application at any stage until rolled up, usually in a substantially amorphous state obtained by rapid cooling after melt extrusion, unstretched ( unoriented) film (A film), then a uniaxially stretched (uniaxially oriented) film (B film) stretched in the longitudinal or transverse direction, or biaxially stretched before heat treatment further stretched in the transverse or longitudinal direction (2 Axial orientation) is applied to any one of the films (C film).

In the present invention, the coating liquid is applied to any one of the A film and the B film before the crystal orientation is completed, and then the film is stretched in the uniaxial direction or the biaxial direction, and heat treatment at a temperature higher than the boiling point of the solvent It is preferable to employ a method of forming a release layer while completing the crystal orientation of the film by carrying out According to this method, since film forming of a film and coating-drying of a resin composition (namely, formation of a mold release layer) can be performed simultaneously, there exists a merit in manufacturing cost.

Especially, the method of apply|coating a coating liquid to the film (B film) uniaxially stretched in the longitudinal direction, and then extending|stretching in the width direction and heat-processing is excellent. Compared to the method of biaxial stretching after coating on an unstretched film, since the stretching step is less than once, defects or cracks in the release layer due to stretching are less likely to occur, and a release layer excellent in smoothness can be formed.

In addition, as described above, by applying the coating liquid to the film before completion of crystal orientation, the adhesion between the release layer and the thermoplastic resin film as the base film can be imparted, and the peel force change P1 before and after the release layer is rubbed. /P2 (peel force (P2) after abrasion treatment/peel force (P1) before abrasion treatment) can be 30 or less.

Therefore, in the present invention, a preferred method of forming the release layer is a method in which a coating liquid using an aqueous solvent is applied on a thermoplastic resin film by an in-line coating method, followed by drying and heat treatment. Furthermore, more preferably, it is a method of in-line-coating the coating liquid on the B film after uniaxial stretching. In the manufacturing method of the laminated|multilayer film of this invention, in order to complete removal of the solvent of a coating liquid, drying can be performed at the temperature range of 80-130 degreeC. In addition, the heat treatment may be performed in a temperature range of 160 to 240° C. in order to complete the crystal orientation of the polyester film and complete the thermal curing of the coating solution to complete the formation of the release layer.

Moreover, it is preferable that solid content concentration of a coating liquid is 40 mass % or less. By making solid content concentration into 40 mass % or less, favorable applicability|paintability can be provided to a coating liquid, and the laminated|multilayer film which has a transparent and uniform mold release layer can be manufactured.

In addition, the solid content concentration represents the ratio of the mass obtained by subtracting the mass of the solvent from the mass of the coating liquid with respect to the mass of the coating liquid (that is, [solid content concentration] = [(mass of the coating liquid)-(mass of the solvent)]/ [mass of coating solution]).

<Method for producing laminated film>

Next, although the case where polyethylene terephthalate (henceforth PET) is used as a thermoplastic resin is demonstrated as an example about the manufacturing method of the laminated|multilayer film of this invention, it is not limited to this.

First, the PET pellets are sufficiently vacuum dried and then supplied to an extruder, melt-extruded into a sheet at about 280° C., and cooled and solidified to produce an unstretched (non-oriented) PET film (A film). This film is stretched 2.5 to 5.0 times in the longitudinal direction with a roll heated to 80 to 120°C to obtain a uniaxially oriented PET film (B film). The coating solution of the present invention prepared at a predetermined concentration is applied to one side of the B film.

At this time, you may surface-treat corona discharge treatment etc. to the coated surface of PET film before application|coating. By performing a surface treatment such as corona discharge treatment, the wettability of the coating liquid to the PET film is improved, and crawling of the coating liquid is prevented, and a release layer having a uniform coating thickness can be formed. After application, the end portion of the PET film is gripped with a clip, guided to a heat treatment zone (preheating zone) at 80 to 130°C, and the solvent of the coating liquid is dried. After drying, stretch 1.1 to 5.0 times in the width direction. Then, it guides to a 160-240 degreeC heat processing zone (heat setting zone), heat processing for 1 to 30 second is performed, and crystal orientation is completed.

In this heat treatment process (heat setting process), you may perform 3 to 15% of relaxation processing in the width direction or the longitudinal direction as needed. Thus, the obtained laminated|multilayer film is excellent in releasability, and is a laminated|multilayer film excellent in smoothness, transferability, and friction resistance.

Moreover, you may add particle|grains to a film raw material in order to give functions, such as running property (lubricity), weather resistance, heat resistance, to a thermoplastic resin film in the range which does not impair the effect of invention. As a material of the particles added to the film raw material, additives, for example, a heat-resistant stabilizer, an oxidation-resistant stabilizer, a weather-resistant stabilizer, an ultraviolet absorber, a lubricant, and the like can be used.

[Methods for measuring characteristics and methods for evaluating effects]

(1) Indentation modulus

After the measurement sample was left still in the environment of 23 degreeC/65%RH for 24 hours, humidity was controlled. After that, the sample is attached to the pedestal so that the surface of the release layer of the measurement sample is facing up, and the load displacement curve is measured from the release layer side using an ultra-micro indentation hardness tester ("ENT-3100" manufactured by Aionycus Co., Ltd.), according to ISO14577-1. Based on this, the indentation elastic modulus was calculated|required. Ten points|pieces were measured with respect to one sample, and the average value was made into the indentation elastic modulus. Measurement conditions are described below. In addition, with respect to the origin detection setting in this measurement, it was decided that the origin is judged at the stage where the moving distance in the air of an indenter became less than 50%.

·Maximum load: 3μN

·Load step: 0.4nN

·Indenter: Triangular weight indenter (ridge angle 115°, diamond indenter)

(2) Measurement of arithmetic mean roughness (Ra)

In the ScanAsyst Air mode of an atomic force microscope manufactured by BRUKER "Dimension Icon ScanAsyst", the release layer side of the laminated film was measured in a measurement range of 10 µm × 10 µm, the number of measurement lines 512, and a measurement rate of 1.0 Hz, and from the obtained surface information, JIS -The arithmetic mean roughness (Ra) was calculated by the method specified in -B-0601-1994. Specifically, "NanoScope Analysis" is used as software, "3rd" of "Flatten Order" is selected, and the bending process in three dimensions is performed. After that, "Roughness" is selected, and the numerical value described in "Image Ra" of the screen is called arithmetic mean roughness.

(3) Tape peeling force (initial: P1)

Regarding the tape peeling force, an adhesive tape (Nitto Denko Co., Ltd. polyester tape No. 31B, width 19 mm) was affixed to a laminated film sample (width 5 cm x length 10 cm) at 5 kg with a rubber roller, and 23° C./65% RH After leaving still for 24 hours in the environment of Shimadzu Corporation, using a universal testing machine "Autograph AG-1S" and a 50N load cell, the measurement was performed by performing a 180° peeling test at a peeling rate of 300 mm/min. The average value of the peeling force in 5-10 sec was computed from the graph of peeling force (N)-test time (sec) obtained by the measurement. This measurement was performed 5 times, the average of 3 times which abbreviate|omitted the maximum value and the minimum value was made into the peeling force of laminated|multilayer film, and the following evaluation was performed. Those of A or more were made favorable, and B was made into the level which does not have a problem practically.

S: Less than 0.1N/50mm

A: More than 0.1N/50mm, less than 0.3N/50mm

B: 0.3N/50mm or more, less than 0.5N/50mm

C: 0.5N/50mm or more.

(4) Tape peeling force (after abrasion treatment: P2)

Regarding the tape peeling force (after abrasion treatment), the surface of the release layer was rubbed 10 reciprocally using a nonwoven fabric (NT-4 manufactured by Ozu Sangyo Co., Ltd.) at a load of 500 g/cm 2 , and the surface of the release layer after the abrasion treatment was rubbed against the surface of the release layer. An adhesive tape (Nitto Denko Co., Ltd. polyester tape No. 31B, width 19 mm) was affixed to a laminated film sample (width 5 cm x length 10 cm) at 5 kg with a rubber roller, and 24 hours at 23°C/65% RH. After standing still, it measured by performing a 180 degree peeling test at a peeling rate of 300 mm/min using Shimadzu Corporation's universal testing machine "Autograph AG-1S" and a 50N load cell. The average value of the peeling force in 5-10 sec was computed from the graph of peeling force (N)-test time (sec) obtained by the measurement. This measurement was performed 5 times, the average of 3 times which abbreviate|omitted the maximum value and the minimum value was made into the peeling force of laminated|multilayer film, and the following evaluation was performed. Those of A or more were made favorable, and B was made into the level which does not have a problem practically.

S: less than 1.0N/50mm

A: 1.0N/50mm or more, 3.0N/50mm or more

B: 3.0N/50mm or more, less than 5.0N/50mm

C: 5.0N/50mm or more.

(5) Change in peel force before and after the release layer was rubbed (P2/P1)

Peel force change P2/P1 before and after the release layer was rubbed and processed was calculated|required from the value of P1 and P2 calculated|required by (1) and (2).

(6) Slurry peel force

Regarding the slurry peeling force, a ceramic slurry mixed with a laminated film sample (width 5 cm × length 10 cm) with the following composition is applied to the release layer side of the laminated film of the present invention to a final thickness of 5 μm using an applicator, 60 A ceramic sheet was formed by drying at &lt;RTI ID=0.0&gt;C/1min.&lt;/RTI&gt;

The ceramic sheet was subjected to a 180° peeling test at a peeling rate of 300 mm/min using a universal testing machine "Autograph AG-1S" manufactured by Shimadzu Corporation and a 50N load cell. The average value of the peeling force in 5-10 sec was computed from the graph of peeling force (N)-test time (sec) obtained by the measurement. This measurement was performed 5 times, the average of 3 times which abbreviate|omitted the maximum value and the minimum value was made into the peeling force of laminated|multilayer film, and the following evaluation was performed. Those of A or more were made favorable, and B was made into the level which does not have a problem practically.

S: less than 0.05N/50mm

A: Less than 0.05~0.1N/50mm

B: Less than 0.1-0.3N/50mm

C: 0.3N/50mm or more.

<Composition of ceramic slurry>

·BaTiO ₃ (manufactured by Sakai Kagaku Kogyo Co., Ltd.) 100 parts by mass

・Polyvinyl butyral (Sekisui Kagaku Kogyo Co., Ltd. "S-Rec (registered trademark)" BL-1) 10 parts by mass

・Phthaldioctyl (manufactured by Kanto Chemical Co., Ltd.) 5 parts by mass

・70 parts by mass of toluene

· Ethanol (manufactured by Tokyo Kasei Co., Ltd.) 50 parts by mass.

(7) Warriorability

About transferability, it is computed as adhesive tape peeling force (P4)/initial stage adhesive tape peeling force (P3) x 100 after sticking/peeling. The measuring method of each peeling force is described below.

(7-1) Initial adhesive tape peeling force (P3)

Adhesive tape (Nitto Denko Co., Ltd. polyester tape No. 31B, width 19 mm) was attached to a stainless plate (No. SUS304) at 5 kg with a rubber roller, left still in an environment of 23° C./65% RH for 24 hours, then Shimadzu ( A 180° peeling test was performed at a peeling rate of 300 mm/min using a universal testing machine manufactured by Note) "Autograph AG-1S" and a 50N load cell. The average value of the peeling force in 5-10 sec was computed from the graph of peeling force (N)-test time (sec) obtained by the measurement. This measurement was performed 5 times, and the average of 3 times which abbreviate|omitted the maximum value and the minimum value was made into initial stage adhesive tape peeling force (P3).

(7-2) Adhesive tape peeling force after attachment/peel off (P4)

An adhesive tape (Nitto Denko Co., Ltd. polyester tape No. 31B, width 19 mm) was affixed at 5 kg with a rubber roller on the release layer side of the laminated film, and after leaving still for 24 hours in an environment of 23° C./65% RH, Shimadzu Co., Ltd. ) A universal testing machine "Autograph AG-1S" and a 50N load cell were used to perform a 180° peel test at a peeling rate of 300 mm/min, and the adhesive tape was peeled off. After that, the peeled adhesive tape was attached to a stainless plate (No. SUS304) and left still in an environment of 23°C/65% RH for 24 hours. A 180° peeling test was performed at a peeling rate of 300 mm/min. The average value of the peeling force in 5-10 sec was computed from the graph of peeling force (N)-test time (sec) obtained by the measurement. This measurement was performed 5 times, and the average of 3 times which abbreviate|omitted the maximum value and the minimum value was made into the adhesive tape peeling force (P4) after sticking/peeling off.

For the peeling force obtained in (7-1) and (7-2), transferability is judged based on the value of adhesive tape peeling force (P4)/initial adhesive tape peeling force (P3) x 100 after attachment/peeling did. When peeling an adhesive tape, it shows that an adhesive does not adhere to a mold release layer, so that this value is high.

Those of A or more were made favorable, and B was made into the level which does not have a problem practically.

S: 95% or more

A: More than 90% and less than 95%

B: 85% or more and less than 90%

C: less than 85%.

(8) Analysis of the composition of the release layer

The composition analysis of the release layer was performed on the surface of the laminated film by X-ray photoelectron spectroscopy (ESCA), Fourier infrared spectrophotometer (FT-IR) ATR method, and time-of-flight secondary ion mass spectrometry (TOF-SIMS). did Further, the release layer was dissolved and extracted with a solvent and separated by chromatography, followed by proton nuclear magnetic resonance spectroscopy ( ¹ H-NMR), carbon nuclear magnetic resonance spectroscopy ( ¹³ C-NMR), and Fourier infrared spectrophotometry (FT-IR). ), the structure was analyzed, thermal decomposition gas chromatography mass spectrometry (GC-MS) was performed, and compositional analysis of the release layer was performed.

By the said method, the hydroxyl-containing compound (B) in a mold release layer was identified.

(9) thickness of the release layer

The laminated film is dyed _{with RuO 4} and/or OsO _{4 .} Next, the laminated film is frozen and cut in the film thickness direction to obtain 10 samples (10 pieces) of ultra-thin slices for cross-sectional observation of the release layer. The cross-section of each sample is observed with a TEM (transmission electron microscope: H7100FA type manufactured by Hitachi Seisakusho Co., Ltd.) at 10,000 to 1 million times to obtain a cross-sectional photograph. The measured value of the mold release layer thickness of the sample of 10 points|pieces (10 pieces) is averaged, and let it be mold release layer thickness of laminated|multilayer film.

(10) Tape peeling force (70℃)

Regarding tape peeling force (after abrasion treatment), a laminated film sample to which an adhesive tape (polyester tape No. 31B manufactured by Nitto Denko Co., Ltd., 19 mm wide) was applied was left still in an environment of 70°C and 40% RH for 24 hours, followed by a peel test. Except for performing the measurement, similarly to (3), the peel force was calculated, and the following evaluation was performed.

Those of A or more were made favorable, and B was made into the level which does not have a problem practically.

S: Less than 0.1N/50mm

A: More than 0.1N/50mm, less than 0.3N/50mm

B: 0.3N/50mm or more, less than 0.5N/50mm

C: 0.5N/50mm or more.

Example

Next, although this invention is demonstrated based on an Example, this invention is not limited to these. In addition, the synthesis method of the silicone resin (A) emulsion and the synthesis method of the acrylic resin (C) emulsion are shown in a reference example.

(Reference Example 1) Preparation of silicone resin (A-1) emulsion

The following resin components were put into an emulsifying device and uniformly mixed and stirred.

200 parts by mass of polydimethylsiloxane (vinyl group content of 0.60 mol/100 g) having at least two unsaturated groups in one molecule as polysiloxane resin (A-a) having at least two unsaturated groups in the molecule;

A hydrogen polysiloxane resin (Ab) having at least two hydrogen atoms directly bonded to a silicon atom in one molecule, a methylhydrogenpolysiloxane having trimethylsilyl groups capped at both ends represented by the following average composition formula-2 (SiH group content 1.20 mol/ 100 g) of 150 parts by mass,

- 600 mass parts of polydimethylsiloxane (vinyl group content 0.02 mol/100g) represented by the following average composition formula-3 as a polysiloxane resin (A-c) which has polydimethylsiloxane as a main component

5 parts by weight of ethynylcyclohexanol as a catalyst activity inhibitor

20 parts by mass of polyoxyethylene styrenated phenyl ether (trade name: Neugen EA-137, Daiichi Kogyo Seiyaku Co., Ltd.) (d-1) as a nonionic surfactant

Next, 900 mass parts of water (ion-exchange water, the same hereinafter) was added to this mixture to invert, and it stirred for 30 minutes continuously. Furthermore, this emulsion was transferred to another container, diluted water was added and stirred, and the emulsion of the silicone resin (A-1) of 40 mass % of silicone parts was obtained.

(Reference Example 2) Preparation of silicone resin (A-2) emulsion:

A silicone resin (A-2) emulsion was prepared in the same manner as in Reference Example 1 except that the siloxane component of Reference Example 1 was changed to the following ratio.

- Polysiloxane resin (A-a) having at least two unsaturated groups in one molecule: 600 parts by mass;

· Hydrogenpolysiloxane resin (A-b) having at least two hydrogen atoms directly bonded to silicon atoms in one molecule (A-b): 450 parts by mass;

· Polysiloxane resin (A-c) containing polydimethylsiloxane as a main component: 600 parts by mass

5 parts by weight of ethynylcyclohexanol as a catalyst activity inhibitor

20 parts by mass of polyoxyethylene styrenated phenyl ether (trade name: Neugen EA-137, Daiichi Kogyo Seiyaku Co., Ltd.) (d-1) as a nonionic surfactant

(Reference Example 3) Preparation of silicone resin (A-3) emulsion:

A silicone resin (A-3) emulsion was prepared in the same manner as in Reference Example 1 except that the siloxane component of Reference Example 1 was changed to the following ratio.

- Polysiloxane resin (A-a) having at least two unsaturated groups in one molecule: 170 parts by mass;

· Hydrogenpolysiloxane resin (A-b) having at least two hydrogen atoms directly bonded to silicon atoms in one molecule (A-b): 100 parts by mass;

· Polysiloxane resin (A-c) containing polydimethylsiloxane as a main component: 300 parts by mass

5 parts by weight of ethynylcyclohexanol as a catalyst activity inhibitor

20 parts by mass of polyoxyethylene styrenated phenyl ether (trade name: Neugen EA-137, Daiichi Kogyo Seiyaku Co., Ltd.) (d-1) as a nonionic surfactant

(Reference Example 4) Preparation of silicone resin (A-4) emulsion:

A silicone resin (A-4) emulsion was prepared in the same manner as in Reference Example 1 except that the siloxane component of Reference Example 1 was changed to the following ratio.

- Polysiloxane resin (A-a) having at least two unsaturated groups in one molecule: 100 parts by mass;

· Hydrogenpolysiloxane resin (A-b) having at least two hydrogen atoms directly bonded to silicon atoms in one molecule (A-b): 50 parts by mass;

· Polysiloxane resin (A-c) containing polydimethylsiloxane as a main component: 300 parts by mass

5 parts by weight of ethynylcyclohexanol as a catalyst activity inhibitor

20 parts by mass of polyoxyethylene styrenated phenyl ether (trade name: Neugen EA-137, Daiichi Kogyo Seiyaku Co., Ltd.) (d-1) as a nonionic surfactant

(Reference Example 5) Preparation of acrylic resin (C-1) emulsion

In a nitrogen gas atmosphere and at room temperature (25° C.), 65 mol parts of methyl methacrylate, 25 mol parts of ethyl acrylate, 9 mol parts of acrylic acid, and 1 mol part of N-methylol acrylamide were added, followed by an emulsifier (ADEKA Co., Ltd. "Rear Soap") " ER-30) was added with 7 mol parts and water to obtain a solution 1. Solution 1 was heated up to 60 degreeC under normal temperature (25 degreeC). Then, water was dripped and added continuously over 3 hours, stirring. At the same time, 2 mole parts of a 5 wt% potassium persulfate aqueous solution were continuously added dropwise. After completion|finish of dripping, after stirring for 2 hours, it cooled to 25 degreeC, reaction was complete|finished and the acrylic resin (C-1) emulsion was obtained. In addition, the solid content concentration of the obtained acrylic resin (C-1) emulsion is 35 weight%.

(coating liquid 1)

A mixture of a silicone resin (A-1), a hydroxyl group-containing compound (B) and a platinum catalyst (D) was added to an aqueous solvent in this order and mixed to obtain a coating solution 1. (In the coating solution, the silicone resin ( The mass ratio of A-1) to the hydroxyl group-containing compound (B) and the platinum catalyst (D) is (A-1)/(B)/(D)=100/20/5).

・Silicone resin (A-1) emulsion

-Hydroxy group-containing compound (B) D-glucitol (manufactured by Nacalaitesk Co., Ltd., molar mass 182 g/mol)

・Platinum catalyst (D-1) "CAT-PM-10A" (manufactured by Shin-Etsu Kagaku Kogyo Co., Ltd.)

·Aqueous solvent (G): pure water

(Coating solution 2~14)

The mixture of a silicone resin (A), a hydroxyl-containing compound (B), an acrylic resin (C), and a platinum catalyst (D) was added to an aqueous solvent in this order, and it mixed, and obtained the coating liquids 1-9. Table 1 shows the weight ratios of the silicone resin (A), the hydroxyl group-containing compound (B), the acrylic resin (C), and the platinum catalyst (D) in the coating liquid.

(Example 1)

After drying polyethylene terephthalate, making it 280 degreeC molten state with the extruder, and interposing a gear pump and a filter, it supplied to die|dye and obtained the molten sheet|seat. Further, after forming into a sheet shape, it was rapidly cooled and solidified on a casting drum maintained at a surface temperature of 25°C by electrostatic application. After heating the obtained cast film in a roll group set at 75° C., it was stretched 3.1 times in the longitudinal direction while rapidly heating with a radiation heater from both sides of the film between the stretching section lengths of 100 mm, and then cooled once. Then, after corona-discharge-treating this uniaxially stretched film in air, the coating liquid 1 was apply|coated to the corona-discharge-treated surface.

The uniaxially stretched film to which the coating liquid 1 was apply|coated was guided to the tenter, and after preheating with 100 degreeC hot air, it extended|stretched 3.5 times in the width direction at the temperature of 110 degreeC. The stretched film was subjected to heat treatment with hot air at 230°C within the tenter as it was, and then 5% relaxation treatment was performed in the width direction at the same temperature to obtain a laminated film. The thickness of this laminated|multilayer film was 38 micrometers. Table 2 shows the properties of the obtained laminated film.

(Examples 2, 3, 5, 7, 8, 10-14)

A laminated film was obtained in the same manner as in Example 1 except that the coating liquid described in the table was used. Table 2 shows the properties of the obtained laminated film.

(Examples 4 and 6)

The laminated polyester film was obtained by the method similar to Example 1 except having changed the temperature of heat processing to 200 degreeC using the coating liquid of the table|surface. Table 2 shows the properties of the obtained laminated polyester film.

(Example 9) Coating solution 4 was applied to a 38 μm biaxially stretched polyester film (“Lumiror” T60 manufactured by Toray Co., Ltd.) so that the thickness after drying was 0.3 μm, dried in a hot air oven at 100° C. for 1 minute, 230 It was made to dry for 1 minute in the figure, and the laminated|multilayer film which laminated|stacked the release layer was obtained. Table 1 shows the weight composition of each resin in the coating liquid 9. In addition, the characteristic of the obtained laminated|multilayer film is shown in Table 2.

(Comparative Example 1)

A laminated film was obtained in the same manner as in Example 1 except that the coating composition described in the table was used. Table 2 shows the properties of the obtained laminated film.

In the laminated film of Comparative Example 1, since the arithmetic surface roughness (Ra) of the release layer exceeded 50 nm, the tape peeling force was at a level at which there was a problem in use as a release film.

(Comparative Example 2)

A laminated film was obtained in the same manner as in Example 4 except that the coating liquid described in the table was used. Table 2 shows the properties of the obtained laminated film.

Since the laminated|multilayer film of Comparative Example 2 had an indentation elastic modulus of a release layer of less than 100 N/mm<2>, tape peeling force was a level with a problem in use as a release film.

(Comparative Example 3)

A laminated film was obtained in the same manner as in Example 1 except that the coating liquid described in the table was used. Table 2 shows the properties of the obtained laminated film.

Since the laminated|multilayer film of the comparative example 3 did not have a silicone resin in a release layer, the tape peeling force was a level with a problem in use as a release film.

(Industrial Applicability)

Since the laminated film of the present invention is excellent in releasability to an adhesive or releasability to a ceramic slurry, and excellent in smoothness, transferability, and friction resistance, it is suitable for producing protective films for adhesive films, various ceramic sheets, and the like. It can be used suitably as a carrier film.

Claims (11)

A laminated film having a thermoplastic resin film and a resin layer containing a silicone resin (the resin layer is referred to as a release layer), wherein the release layer is in at least one outermost layer of the laminated film, and the press-fitting measured from the release layer side The elastic modulus is 100N/mm2 or more, and the arithmetic mean roughness (Ra) of the surface of the release layer is 1 to 50 nm,
The laminated|multilayer film whose content of the silicone resin contained in the said mold release layer is 50 weight% or more with respect to the whole mold release layer. The method of claim 1,
The laminated|multilayer film whose peeling force change (peel force (P2) after abrasion process / peeling force (P1) before abrasion process) before and after carrying out the said release layer rubbing process is 30 or less. The method of claim 1,
The laminated film whose indentation elastic modulus measured by the said release layer side is 1000 N/mm<2> or more and 5000 N/mm<2> or less. 4. The method of claim 1 or 3,
The laminated film in which resin which comprises the said mold release layer contains two or more hydroxyl groups in 1 molecule, and contains the hydroxyl-containing compound whose molar mass is 300 g/mol or less. 5. The method of claim 4,
The content of the silicone resin contained in the release layer is 60% by weight or more with respect to the entire release layer, and the content of the hydroxyl group-containing compound contained in the release layer is 5 to 40 parts by weight when the silicone resin is 100 parts by weight. 5. The method of claim 4,
The said hydroxyl-containing compound is a laminated|multilayer film containing at least 1 sort(s) of compound selected from glycol, a sugar alcohol, and a sugar alcohol derivative. 4. The method of claim 1 or 3,
The laminated|multilayer film whose said silicone resin is an addition-curable silicone resin. 4. The method of claim 1 or 3,
A laminated film having a release layer directly on at least one side of the thermoplastic resin film. A method for producing the laminated film according to claim 1 or 3, comprising:
A coating liquid containing a silicone resin is applied to at least one side of the thermoplastic resin film before crystal orientation is completed, and then the thermoplastic resin film is stretched in at least one axial direction, and the thermoplastic resin film is subjected to heat treatment to heat the thermoplastic resin. The manufacturing method of the laminated|multilayer film including the process of completing the crystal orientation of a film. 10. The method of claim 9,
The manufacturing method of the laminated|multilayer film containing the hydroxyl-containing compound whose molar mass is 300 g/mol or less which contains 2 or more hydroxyl groups in 1 molecule in the said coating liquid. 11. The method of claim 10,
The manufacturing method of the laminated|multilayer film whose boiling point of the said hydroxyl-containing compound is 200 degreeC or more.